Polymerizable composition containing novel cyclic sulfur compound and resin obtained by curing the polymerizable composition

ABSTRACT

A sulfur-containing compound has a structure represented by formula (1):  
                 
 
(wherein R1 represents a hydrogen atom, a reactive terminal group, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms and a reactive terminal group or its thia derivative thereof, an aryl group, or an aralkyl group; Y represents an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom; R represents a substituted or unsubstituted bivalent hydrocarbon group having 1 to 10 carbon atoms, which may be thianated; n represents an integer of 0 to 3; X 1  is substituted for any one of groups R2 to R7 of a partial structure represented by formula (2) in which the groups R2 to R7 other than the group substituted by X 1  are independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; and R1 is not a group having a (meth)acryl group when Y is an oxygen atom.)  
                 
The compound has a high refractive index and high Abbe&#39;s number, and produces a resin having excellent impact resistance.

TECHNICAL FIELD

The present invention relates to a sulfur-containing cyclic compoundwhich can be suitably used in the field of optical material resins andthe like required to have a high refractive index and high transparency.The present invention also relates to a polymerizable compositioncontaining the sulfur-containing cyclic compound, a resin and opticalmaterial produced by polymerization curing of the composition, and amethod for producing a resin by curing the composition.

BACKGROUND ART

Plastic lenses have recently rapidly been widespread as opticalmaterials for eyeglasses, camera lenses, and the like because theplastic lenses are lightweight and less broken and can be dyed, ascompared with inorganic lenses.

The performances required for the plastic lenses include opticalperformances such as a high refractive index and a high Abbe's number,and physical and chemical properties such as high impact resistance,ease of dyeing, no problem about heat resistance, and a low specificgravity. The performances further include the property that the lensproducing method and monomer compound used have safety of the human bodyand ease of handling.

Of these performances, high heat resistance and a low specific gravityare realized at a high level even by using an existinghigh-refractive-index plastic lens. An example of resins which arecurrently used for a variety of plastic lenses is a resin produced byradical polymerization of diethylene glycol bis(allyl carbonate)(referred to as “D. A. C” hereinafter). This resin has variousproperties such as excellent impact resistance, a light weight,excellent dyeing performance, good processability such as cuttingability, polishing ability, and the like, etc. However, this resin has arefractive index nd of as low as about 1.50, and thus the centralthickness and edge thickness of a plastic lens are increased. Therefore,a resin having a higher refractive index is demanded for the plasticlenses.

Known examples of a resin having a higher refractive index than that ofthe D. A. C resin include sulfur atom-containing resins such as apolythiourethane resin, a sulfur-containing o-(meth)acrylate resin, andthio(meth)acrylate resin. The polythiourethane resin is a well-balancedresin having a high refractive index, excellent impact resistance,excellent dyeing performance, and the like. For other resins having ahigh refractive index and high Abbe's number, a method using apolyepisulfide compound is proposed (refer to, for example, PublicationNo. WO89/10575, Japanese Unexamined Patent Application Publication Nos.9-110979 and 11-322930).

Also, a method of adding a known sulfur-containing compound to apolyepidithio compound or polyepisulfide compound is proposed forachieving a higher refractive index. However, the producing method andidentification data for the compound are not described in examples, anda method of adding a known sulfur-containing compound to thepolyepisulfide compound decreases the crosslinking property of a resinto decrease heat resistance. Therefore, this method has lowpracticability (refer to, for example, Japanese Unexamined PatentApplication Publication Nos. 2000-281787, 2001-002783, and 2002-040201).

In the above-described method of adding a known sulfur-containingcompound to the polyepisulfide compound, an example of compounds to beadded is a monofunctional thietane compound. A typical known example ofthe thietane compound is methacryloyloxyalkylthietane which is used as aphotopolymerizable compound for a photosensitive composition. Thiscomposition has a low refractive index and no transparency, and thuscannot be used for some optical applications required to have such ahigh refractive index as in the present invention (refer to, forexample, Japanese Unexamined Patent Application Publication Nos.55-066909 and 59-180544).

In the above-described conditions, the proposed method using thepolyepisulfide compound having a high refractive index and high Abbe'snumber in a well-balanced state has been advanced to practical use.However, the method causes a handling problem due to the low thermalstability of the polyepisulfide compound in some cases. In order tosolve the problem, a method for improving the thermal stability of thepolyepisulfide compound is required, and various methods have beenproposed. However, any one of the proposed methods is not satisfactory(refer to, for example, Japanese Unexamined Patent ApplicationPublication No. 11-256038).

Furthermore, a resin produced by curing the polyepisulfide compound isbrittle, and thus cannot be subjected to special processing such astwo-point processing or the like, particularly, in the application toeyeglasses. Also, in some cases, there is the problem of cracking a lensin releasing after casting polymerization. Furthermore, in some of theapplications to eyeglasses required to have safety, necessary physicalproperties are not sufficiently satisfied because of the low impactresistance of the resin. Therefore, various methods have been proposedfor improving the resin, but any one of the methods is unsatisfactory(refer to, for example, Japanese Unexamined Patent ApplicationPublication Nos. 2001-131257).

In a condition in which a plastic lens is required to have a higherrefractive index and higher Abbe's number, it is greatly demanded topropose a novel compound which can be replaced with the polyepisulfidecompound, which has a high refractive index and high Abbe's number, andwhich permits improvements in brittleness and impact resistance.

Therefore, the inventors conducted studies for improving the refractiveindex of a compound different from the polyepisulfide compound withoutdecreasing the Abbe's number to provide a material complying with therequirements of a higher refractive index and higher Abbe's number.

DISCLOSURE OF THE INVENTION

As a result of intensive research for solving the above problems, theinventors found that a resin produced by curing a compound having astructure represented by formula (1), i.e., a sulfur-containing cyclicskeleton, has not only a high refractive index and high Abbe's numberand excellent optical physical properties but also low brittleness andexcellent impact resistance. The inventors also found that the compoundis excellent in thermal stability as compared with the currentlyproposed polyepisulfide compound, leading to the achievement of thepresent invention.

The present invention includes the following matters:

[1] A sulfur-containing compound has a structure represented by formula(1).

(wherein R1 represents a hydrogen atom, a reactive terminal group, astraight, branched or cyclic alkyl group having 1 to 10 carbon atoms anda reactive terminal group or its thia derivative, an aryl group, or anaralkyl group; Y represents an oxygen atom, a sulfur atom, a seleniumatom, or a tellurium atom; R represents a substituted or unsubstitutedbivalent hydrocarbon group having 1 to 10 carbon atoms, which may bethianated; n represents an integer of 0 to 3; X₁ is substituted for anyone of groups R2 to R7 of a partial structure represented by formula (2)in which the groups R2 to R7 other than the group substituted by X₁ areindependently a hydrogen atom or a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 10 carbon atoms; and R1 is nota group having a (meth)acryl group when Y is an oxygen atom.)

[2] The sulfur-containing cyclic compound [1] has a structurerepresented by formula (3).

(wherein R1 represents a hydrogen atom, a reactive terminal group, astraight, branched or cyclic alkyl group having 1 to 10 carbon atoms anda reactive terminal group or its thia derivative, an aryl group, or anaralkyl group; R2 to R6 independently represent a hydrogen atom or asubstituted or unsubstituted monovalent hydrocarbon group having 1 to 10carbon atoms; R represents a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms, which may be thianated; nrepresents an integer of 0 to 3; Y represents an oxygen atom, a sulfuratom, a selenium atom, or a tellurium atom; and R1 is not a group havinga (meth)acryl group when Y is an oxygen atom.)

[3] The sulfur-containing cyclic compound [1] or [2] has a structurerepresented by formula (4).

(wherein Q represents a hydrogen atom, a straight, branched or cyclicalkyl group having 1 to 10 carbon atoms and a reactive terminal group orits thia derivative, an aryl group, or an aralkyl group; R represents asubstituted or unsubstituted divalent hydrocarbon group having 1 to 10carbon atoms, which may be thianated; and n represents an integer of 0to 3.)

[4] Any one of the sulfur-containing cyclic compounds [1] to [3] is3-mercaptothietane, 3-(acryloylthio)thietane,3-(methacryloylthio)thietane, 3-(2,3-epithiopropylthio)thietane,3-(allylthio)thietane, 3-(isocyanatomethylthio)thietane,3-(aminoethylthio)thietane, or 3-(isothiocyanatoethylthio)thietane.

[5] Any one of the sulfur-containing compounds [1] to [3] has astructure represented by formula (5).

(wherein R′ and R″ independently represent a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,which may be thianated; U represents a substituted or unsubstitutedstraight, branched or cyclic alkylene group having 1 to 10 carbon atoms,an arylene group, or an aralkylene group, which may be thianated; eachof V and W represents an oxygen atom, a sulfur atom, a selenium atom, ora tellurium atom; 1 represents an integer of 0 to 2; o represents aninteger of 1 to 4; n1 and n2 independently represent an integer of 0 to3; q represents an integer of 0 or 1; X₂ is substituted for any one ofgroups R9 to R14 of a partial structure represented by formula (6), andX₃ is substituted for any one of groups R15 to R20 of the partialstructure represented by formula (6) in which the groups R9 to R20 otherthan the groups substituted by X₂ and X₃ are independently a hydrogenatom or a substituted or unsubstituted monovalent hydrocarbon grouphaving 1 to 10 carbon atoms.)

[6] Any one of the sulfur-containing cyclic compounds [1] to [3] and [5]is represented by formula (7).

(wherein R9 to R19 independently represent a hydrogen atom, asubstituted or unsubstituted monovalent hydrocarbon group having 1 to 10carbon atoms; R′ and R″ independently represent a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,which may be thianated; U represents a substituted or unsubstitutedstraight, branched or cyclic alkylene group having 1 to 10 carbon atoms,an arylene group, or an aralkylene group, which may be thianated; eachof V and W represents an oxygen atom, a sulfur atom, a selenium atom, ora tellurium atom; 1 represents an integer of 0 to 2; o represents aninteger of 1 to 4; n1 and n2 independently represent an integer of 0 to3; and q represents an integer of 0 or 1.)

[7] Any one of the sulfur-containing cyclic compounds [1] to [3] or [5]and [6] is represented by formula (8).

(wherein R″′ represents a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms, which may be thianated; Urepresents a substituted or unsubstituted straight, branched or cyclicalkylene group having 1 to 10 carbon atoms, an arylene group, or anaralkylene group, which may be thianated; 1 represents an integer of 0to 2; o represents an integer of 1 to 4; n represents an integer of 0 to3; and q represents an integer of 0 or 1.)

[8] Any one of the sulfur-containing cyclic compounds [1] to [3] or [5]to [7] is bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide,bis(3-thietanylthio) methane, bis(3-thietanylthiomethyl) sulfide,1,4-bis(3-thietanylthiomethyl) benzene, 1,3-bis(thietanylthiomethyl)benzene, 1,2-bis(thietanylthiomethyl) benzene,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,1,3-bis(3-thietanylthio)propane-1-one, or1,3-bis(3-thietanylthio)propane-1-one-2-methyl.

[9] Any one of the sulfur-containing cyclic compounds [1] to [8] isderived from 3-thiethanol and/or 3-halogenothietane and/or3-mercaptothietane.

[10] A polymerizable composition containing any one of the compounds [1]to [9].

[11] A resin is produced by curing the polymerizable composition [10].

[12] An optical material comprises the resin [11].

[13] A method for producing a resin comprises cast-polymerizing thepolymerizable composition [11].

[14] A method for producing a resin comprises curing a resin by usingthe polymerizable composition [10] as a curing catalyst, and at leastone compound selected from boron trihalides and complexes thereof,trihalogenomethane sulfonic acids and esters and anhydrides thereof.

[15] A method for producing a resin comprises curing a resin by usingthe polymerizable composition [10] as a resin modifier, and at least onecompound selected from compounds each having at least one SH groupand/or NH group and/or NH₂ group.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

In the present invention, a sulfur-containing cyclic compound means acompound having at least one partial structure represented by formula(9).

(wherein each of R21 to R26 represents a hydrogen atom or a substitutedor unsubstituted hydrocarbon group having 1 to 10 carbon atoms.)

Namely, the sulfur-containing cyclic compound is represented by formula(1).

(wherein R1 represents a hydrogen atom, a reactive terminal group, astraight, branched or cyclic alkyl group having 1 to 10 carbon atoms anda reactive terminal group or its thia derivative, an aryl group, or anaralkyl group; Y represents an oxygen atom, a sulfur atom, a seleniumatom, or a tellurium atom; R represents a substituted or unsubstitutedbivalent hydrocarbon group having 1 to 10 carbon atoms, which may bethianated; n represents an integer of 0 to 3; and X₁ is substituted forany one of groups R2 to R7 of a partial structure represented by formula(2) in which the groups R2 to R7 other than the group substituted by X₁are independently a hydrogen atom or a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 10 carbon atoms.)

Substituted or unsubstituted monovalent hydrocarbon groups representedby R2 to R7 and each having 1 to 10 carbon atoms include a straight,branched or cyclic alkyl group, a straight, branched or cyclic alkenylgroup, an aryl group and an aralkyl group. Each of R2 to R7 ispreferably a hydrogen atom or a straight, branched or cyclic alkyl grouphaving 1 to 10 carbon atoms, and more preferably a hydrogen atom.

Examples of a substituted or unsubstituted divalent hydrocarbon grouprepresented by R and having 1 to 10 carbon atoms include a straight,branched or cyclic alkylene group, a straight, a branched or cyclicalkenyl group, an arylene group, and aralkylene group.

Y represents any one of an oxygen atom, a sulfur atom, a selenium atom,and a tellurium atom, and Y is preferably a sulfur atom.

R1 represents a hydrogen atom, a reactive terminal group, a straight,branched or cyclic alkyl group having 1 to 10 carbon atoms and areactive terminal group or a thia derivative thereof, an aryl group, oran aralkyl group. Examples of a reactive terminal group includepolymerizable reactive groups such as a thietanyl group, an episulfidegroup, an alkyleneoxido(thio) group, a —Z—H group (wherein Z representsan oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom), aniso(thio)cyanato group, an amino group, a (thio)(meth)acryl group, analkenyl(thio) group, and the like. Preferred examples include athietanyl group, a thietanylthio group, an oxetanyl group, anoxetanylthio group, an episulfide group, an epoxy group, a mercaptogroup, a hydroxyl group, an iso(thio)cyanato group, an amino group, a(thio)(meth)acryl group, a vinyl(thio) group, an allyl(thio) group, andan isopropenyl group. Particularly, a thietanyl group, a thietanylthiogroup, an episulfide group, a mercapto group, an isothiocyanato group, athio(meth)acryl group, a vinylthio group, and an allylthio group arepreferred. The number of the reactive terminal group is not limited toone, and a plurality of reactive terminal groups may be contained. WhenR1 is a reactive terminal group, R1 is preferably a thietanyl group, anoxetanyl group, an episulfide group, an epoxy group, a vinyl group, anallyl group, an acryl group, or a methacryl group.

The compound represented by formula (1) is preferably a compoundrepresented by formula (3) in which R7 is substituted by X₁.

(wherein R2 to R6 independently represent a hydrogen atom or asubstituted or unsubstituted monovalent hydrocarbon group having 1 to 10carbon atoms; R represents a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms, which may be thianated; nrepresents an integer of 0 to 3; Y represents a sulfur atom, a seleniumatom, or a tellurium atom; and R1 represents a hydrogen atom, a reactiveterminal group, a straight, branched or cyclic alkyl group having 1 to10 carbon atoms and a reactive terminal group or a thia derivativethereof, an aryl group, or an aralkyl group.)

The compound represented formula (3) is preferably a 3-thietane compoundrepresented by formula (4) in which Y is a sulfur atom.

(wherein Q represents a hydrogen atom, a straight, branched or cyclicalkyl group having 1 to 10 carbon atoms and a reactive terminal group ora thia derivative thereof, an aryl group, or an aralkyl group; Rrepresents a substituted or unsubstituted divalent hydrocarbon grouphaving 1 to 10 carbon atoms, which may be thianated; and n represents aninteger of 0 to 3.)

In the present invention, a compound having two or more structuresrepresented by formula (8) is preferred for providing a resin having ahigh refractive index and excellent optical physical properties. Namely,a sulfur-containing cyclic compound represented by formula (5) ispreferred.

(wherein R′ and R″ independently represent a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,which may be thianated; U represents a substituted or unsubstitutedstraight, branched or cyclic alkylene group having 1 to 10 carbon atoms,an arylene group, or an aralkylene group, which may be thianated; eachof V and W represents an oxygen atom, a sulfur atom, a selenium atom, ora tellurium atom; 1 represents an integer of 0 to 2; o represents aninteger of 1 to 4; n1 and n2 independently represent an integer of 0 to3; q represents an integer of 0 or 1; X₂ is substituted for any one ofgroups R9 to R14 of a partial structure represented by formula (6), andX₃ is substituted for any one of groups R15 to R20 of the partialstructure represented by formula (6) in which the groups R9 to R20 otherthan. the groups substituted by X₂ and X₃, respectively, areindependently a hydrogen atom or a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 10 carbon atoms.)

In formula (6), R9 to R20 are defined to have the same meaning as R1 toR6 in formula (1), and R′ and R″ are defined to have the same meaning asR in formula (1).)

In formula (6), preferably, R14 is substituted by X₂, and R20 issubstituted by X₃, as shown by a compound represented by formula (7).

(wherein R9 to R19 independently represent a substituted orunsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms;R′ and R″ independently represent a substituted or unsubstituteddivalent hydrocarbon group having 1 to 10 carbon atoms, which may bethianated; U represents a substituted or unsubstituted straight,branched or cyclic alkylene group having 1 to 10 carbon atoms, anarylene group, or an aralkylene group, which may be thianated; each of Vand W represents an oxygen atom, a sulfur atom, a selenium atom, or atellurium atom; 1 represents an integer of 0 to 2; o represents aninteger of 1 to 4; n1 and n2 independently represent an integer of 0 to3; and q represents an integer of 0 or 1.)

Each of V and W represents any one of an oxygen atom, a sulfur atom, aselenium atom, and a tellurium atom, and preferably a sulfur atom.

U is preferably a straight, branched or cyclic alkylene group having 1to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or anaralkylene group having 7 to 10 carbon atoms, and a methylene group ofan alkyl component in an alkylene or aralkylene group may be partiallythianated with sulfur. Examples of such groups include divalent groupsderived from straight alkanes such as methane, ethane, propane, butane,and the like; divalent groups derived from branched alkanes such asisopropane, sec-butane, tert-butane, sec-pentane, neo-pentane, and thelike; divalent groups derived from cyclic alkanes such as cyclopentane,cyclohexane, and the like; divalent groups derived from straight orbranched thiaalkanes such as 3-thiapentane, 4-thiahexane,3,6-dithiaoctane, 3,6,9-trithiaundecane, and the like; divalent groupsderived from cyclic thiaalkanes such as 1,4-dithiane, 1,3-dithiane,1,3-dithiolane, 1,3-dithietane, and the like; divalent groups derivedfrom unsubstituted or alkyl-substituted benzenes such as benzene,toluene, xylene, and the like; divalent groups derived from aromaticheterocycles such as thiophene and the like.

U may be substituted by the reactive terminal group or analkylenesulfido(thio) group except an episulfide group. Particularly, Umay have 1 to 3 thietanyl groups or thietanylthio groups assubstituents. Namely, the present invention includes tri- orhigher-functional sulfur-containing cyclic compounds.

1 represents an integer of 0 to 2. For example, when U is phenylene, and1 is 2, the compound contains biphenylene.

Particularly, the compound represented by formula (7) preferably has astructure represented by formula (8).

(wherein R′″ is defined to have the same meaning as R′ and R″, U, l, o,and q are defined to have the same meaning as described above, and nrepresents an integer of 0 to 3.)

Examples of the compound having the structure represented by formula (8)include chain aliphatic 3-thietanyltio compounds such as1,1-bis(3-thietanylthio)methane, 1,2-bis(3-thietanylthio)ethane,1,2-bis(3-thietanylthio)propane, 1,3-bis(3-thietanylthio)propane,1,3-bis(3-thietanylthio)-2-methylpropane,1,4-bis(3-thietanylthio)butane, 1,4-bis(3-thietanylthio)-2-methylbutane,1,3-bis(3-thietanylthio)butane, 1,5-bis(3-thietanylthio)pentane,1,5-bis(3-thietanylthio)-2-methylpentane,1,5-bis(3-thietanylthio)-3-thiapentane, 1,6-bis(3-thietanylthio)hexane,1,6-bis(3-thietanylthio)-2-methylhexane,3,8-bis(3-thietanylthio)-3,6-dithiaoctane,1,2,3-tris(3-thietanylthio)propane,2,2-bis(3-thietanylthio)-1,3-bis(3-thietanylthio)propane,2,2-bis(3-thietanylthio)-1-(3-thietanylthio)butane,1,5-bis(3-thietanylthio)-2-(3-thietanylthiomethyl)-3-thiapentane,1,5-bis(3-thietanylthio)-2,4-bis(3-thietanylthiomethyl)-3-thiapentane,1-(3-thietanylthio)-2,2-bis(3-thietanylthiomethyl)-4-thiahexane,1,5,6-tris(3-thietanylthio)-4-(3-hietanylthiomethyl)-3-thiahexane,1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane,1,8-bis(3-thietanylthio)-4,5-bis(3-thietanylthiomethyl)-3,6-dithiaoctane,1,8-bis(3-thietanylthio)-4,4-bis(3-thietanylthiomethyl)-3,6-dithiaoctane,1,8-bis(3-thietanylthio)-2,5-bis(3-thietanylthiomethyl)-3,6-dithiaoctane,1,8-bis(3-thietanylthio)-2,4,5-tris(3-thietanylthiomethyl)-3,6-dithiaoctane,1,1,1-tris[[2-(3-thietanylthio)ethyl]thiomethyl]-2-(3-thietanylthio)ethane,1,1,2,2-tetrakis[[2-(3-thietanylthio)ethyl]thiomethyl]ethane,1,11-bis(3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,1,1,3,3-tetrakis(3-thietanylthiomethylthio)propane,1,1,2,2-tetrakis(3-thietanylthiomethylthio)ethane,3-(3-thietanylthiomethyl)-1,5-di(3-thietanylthio)-2,4-dithiapentane, andthe like; cyclic aliphatic 3-thietanylthio compounds such as1,3-bis(3-thietanylthio)cyclohexane,1,4-bis(3-thietanylthio)cyclohexane,1,3-bis(3-thietanylthiomethyl)cyclohexane,1,4-bis(3-thietanylthiomethyl)cyclohexane,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,4,6-bis(3-thietanylthiomethyl)-1,3-dithiane,4,5-bis(3-thietanylthiomethyl)-1,3-dithiolane,2,4-bis(3-thietanylthiomethyl)-1,3-dithietane,2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane,2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane,2-bis(3-thietanylthio)methyl-1,3-dithiolane, and the like; aromatic3-thietanylthio compounds such as 1,2-bis(3-thietanylthio)benzene,1,3-bis(3-thietanylthio)benzene, 1,4-bis(3-thietanylthio)benzene,1,2-bis(3-thietanylthiomethyl)benzene,1,3-bis(3-thietanylthiomethyl)benzene,1,4-bis(3-thietanylthiomethyl)benzene,bis[4-(3-thietanylthio)phenyl]methane,2,2-bis[4-(3-thietanylthio)phenyl]propane,bis[4-(3-thietanylthio)phenyl]sulfide,bis[4-(3-thietanylthio)phenyl]sulfone,4,4′-bis(3-thietanylthio)biphenyl, and the like; asymmetric compoundssuch as 1,3-bis(3-thietanylthio)propane-1-one, 1,3-bis(3-thietanylthio)-2-methylpropane-1-one, and the like. However, the compounds are notlimited to these examples. of these compound examples, preferredcompounds include 1,1-bis(3-thietanylthio)methane,1,2-bis(3-thietanylthio)ethane, 1,2,3-tris(3-thietanylthio)propane,1,8-bis(3-thietanylthio)-4-(3-thietanylthiomethyl)-3,6-dithiaoctane,1,11-bis (3-thietanylthio)-4,8-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(3-thietanylthio)-4,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(3-thietanylthio)-5,7-bis(3-thietanylthiomethyl)-3,6,9-trithiaundecane,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,2,5-bis[[2-(3-thietanylthio)ethyl]thiomethyl]-1,4-dithiane,2,5-bis(3-thietanylthiomethyl)-2,5-dimethyl-1,4-dithiane,4,5-bis(3-thietanylthiomethyl)-1,3-dithiolane,2,4-bis(3-thietanylthiomethyl)-1,3-dithietane, and2-bis(3-thietanylthio)methyl-1,3-dithiolane. More preferred compoundsinclude bis(3-thietanylthio)methane, bis(3-thietanylthiomethyl)sulfide,and 2-bis(3-thietanylthio)methyl-1,3-dithiolane.

The sulfur-containing cyclic compound represented by formula (1) of thepresent invention can be derived from, for example, a3-hydroxy(alkyl)thietane compound represented by formula (10).

(wherein R represents a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms, which may be thianated,and n represents an integer of 0 to 3.)

Examples of a compound having a structure represented by formula (10)include alkylthietane compounds such as 3-thietanol,3-hydroxymethylthietane, 3-hydroxyethylthietane,3-hydroxypropylthietane, 3-hydroxyisopropylthietane, and the like;sulfur-containing hydroxythietane compounds such as3-hydroxyethylthiothietane, and the like. However, the compounds are notlimited to these examples.

A typical example is 3-thietanol that can easily be synthesized by aknown method. For example, epihalohydrin and an alkali may besimultaneously charged in an alcohol or water saturated with dissolvedhydrogen sulfide. As the alcohol, any alcohol may be used as long ashydrogen sulfide can be dissolved therein. However, methanol having highdissolving power is preferred. As the epihalohydrin, epichlorohydrin andepibromohydrin are preferred. As the alkali, either an inorganic ororganic alkali may be used. Preferred examples of the alkali includealkali metal or alkali earth metal hydroxides, alkali metal or alkaliearth metal carbonates, alkali metal or alkali earth metal bicarbonates,ammonia, tertiary amines, secondary amines, primary amines, metalalkoxides, and the like. Another method may be used, in which1-chloro-3-mercaptopropane-2-ol is reacted with an alkali in the absenceof presence of a solvent such as water, an alcohol, or the like.

The 3-hydroxy(alkyl)thietane compound including 3-thiethanol having thestructure represented by formula (10) can be converted into a2-halogeno(alkyl)thietane compound having a structure represented byformula (11) using a halogenating agent or the like.

(wherein X represents a halogen atom such as chlorine, bromine, iodine,or the like, R represents a substituted or unsubstituted straight,branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, and nrepresents an integer of 0 to 3.)

Preferred examples of the halogenating agent include thionyl chloride,phosphorus trichloride, hydrochloric acid, hydrogen chloride, phosphorustribromide, hydrobromic acid, hydrogen bromide, chlorine, bromine, andthe like. However, the halogenating agents are not limited to theseexamples. Although the solvent used in the reaction depends upon thetype of the halogenating agent used, the solvent need not be used in thereaction, or any solvent may be used as long as it does not inhibithalogenation and does not react with the halogenating agent. Althoughthe reaction temperature also depends upon the type of the halogenatingagent used, good results are obtained with the reaction temperature of−30° C. to 50° C. in some cases, and the reaction temperature ispreferably −10° C. to 30° C.

Examples of the compound having the structure represented by formula(11) include halogeno(alkyl)thietane compounds such as 3-chlorothietane,3-chloromethylthietane, 3-chloroethylthietane, 3-chloropropylthietane,3-chloroisopropylthietane, and the like; compounds having bromo groupssubstituted for the chloro groups of the chloro(alkyl)thietanecompounds; compounds having iodo groups substituted for the chlorogroups of the chloro(alkyl)thietane compounds; sulfur-containinghalogeno(alkyl)thietane compounds such as 3-chloroethylthiothietane, andthe like. The compounds are not limited to these examples.

Of compounds (formula (5)) each having two or more structuresrepresented by formula (9), a compound represented by formula (7) havingat least two thietanyl groups can be synthesized by, for example, thefollowing method.

The 3-halogeno(alkyl)thietane compound having the structure representedby formula (11) is reacted with a alkali sulfide such as sodium sulfide,disodium disulfide, disodium trisulfide, disodium tetrasulfide,potassium sulfide, dipotassium disulfide, dipotassium trisulfide,dipotassium tetrasulfide, or the like to synthesize bis(3-thietanylakly)sulfide, bis(3-thietanylalkyl) disulfide, bis(3-thietanylalkyl)trisulfide, bis(3-thietanylalkyl) tetrasulfide, or the like. Therefore,bis(3-thietanyl) sulfide, bis(3-thietanyl) disulfide, bis(3-thietanyl)trisulfide, bis(3-thietanyl) tetrasulfide, or the like can besynthesized from 3-halogenothietane. Although the solvent used for thereaction depends upon the type of a compound to be synthesized, nosolvent or the use of a solvent which can dissolve the reaction product,such as a hydrocarbon compound, an aromatic compound, a halogenatedcompound, an ester compound, an ether compound, a ketone compound, orthe like produces good results in some cases. Although benzene, toluene,diethyl ether, methyl ethyl ketone, methyl isobutyl ketone, or the likeis preferably used, the solvents are not limited to these compounds.Although the reaction temperature also depends upon the type of thecompound to be synthesized, the reaction temperature of −30° C. to 100°C. generally produces good results in some cases. The reactiontemperature is preferably −10° C. to 50° C., and more preferably 0° C.to 30° C.

The target sulfur-containing cyclic compound can be synthesized byreacting 3-halogeno(alkyl)thietane with a known polythiol compound. Inan example of a synthetic method, 3-halogeno(alkyl)thietane is mixedwith a polythiol compound in the presence or absence of the solvent, andan alkali such as an inorganic alkali, a metal alkoxide, an organicamine, or the like is added to the resultant mixture. Another examplecomprises mixing and reacting 3-halogeno(alkyl)thietane with a solutionof a metal salt of a polythiol compound in which its thiol groups arereacted with an inorganic alkali or metal alkoxide. The quantitativeratio of 3-halogeno(alkyl)thietane to the polythiol compound requiredfor the reaction, i.e., the ratio of (halogeno groups of3-halogeno(alkyl)thietane)/(thiol groups of the polythiol compound), istheoretically 1. However, considering the reaction rate and economy, thequantitative ratio is 0.5 to 2, preferably 0.8 to 1.5, and morepreferably 0.9 to 1.2. Although the solvent used for the reactiondepends upon the type of the compound to be synthesized, no solvent orthe use of a solvent which can dissolve the reaction product, such as aninorganic or organic hydrocarbon compound, an aromatic compound, ahalogenated compound, an ester compound, an ether compound, a ketonecompound, or the like produces good results in some cases. Althoughbenzene, toluene, diethyl ether, methyl ethyl ketone, methyl isobutylketone, or the like is particularly preferred, the solvents are notlimited to these compounds. Although the reaction temperature alsodepends upon the type of the compound to be synthesized, the reactiontemperature of −50° C. to 100° C. generally produces good results insome cases. The reaction temperature is preferably −30° C. to 50° C.,and more preferably −10° C. to 30° C.

As the polythiol compound used as a raw material, any one of knownpolythiol compounds may be used. However, preferred examples includealiphatic thiols such as 1,1-methanedithiol, 1,2-ethanedithiol,1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol,1,4-butaneditiol, 1,2,3-trimercaptopropane,tetrakis(mercaptomethyl)methane, 1,2-dimercaptocyclohexane,bis(1-mercaptomethyl) sulfide, bis(2-mercaptoethyl) sulfide,2,3-dimercapto-1-propanol, 1,3-dimercapto-2-propanol, ethyleneglycolbis(3-mercaptopropionate), diethyleneglycol bis(3-mercaptopropionate),diethyleneglycol bis(2-mercaptoglycolate), pentaerythritoltetrakis(2-mercaptothioglycolate), pentaerythritoltetrakis(3-mercaptopropionate), trimethylolpropanetris(2-mercaptothioglycolate), trimethylolpropanetris(3-mercaptopropionate), 1,1,1-trimethylmercaptoethane,1,1,1-trimethylmercaptopropane, 2,5-dimercaptomethyl thiophene,4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,2,5-dimercaptomethyl-1,4-dithiane,2,5-bis[(2-mercaptoethyl)thiomethyl]-1,4-dithiane,1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol,4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,1,1,3,3-tetrakis(mercaptomethylthio)propane,1,1,2,2-tetrakis(mercaptomethylthio)ethane,3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane,tris(mercaptomethylthio)methane, 4,6-dimercapto-1,3-dithiane, and thelike; aromatic thiols such as 1,2-dimercaptobenzene,1,3-dimercaptobenzene, 1,4-dimercaptobenzene,1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene,1,4-bis(mercaptomethyl)benzene, 2,2′-dimercaptobiphenyl,4,4′-dimercaptobiphenyl, bis(4-mercaptophenyl)methane,bis(4-mercaptophenyl) sulfide, bis(4-mercaptophenyl) sulfone,2,2-bis(4-mercaptophenyl)propane, 1,2,3-trimercaptobenzene,1,2,4-trimercaptobenzene, 1,2,5-trimercaptobenzene, and the like.However, the polythiol compounds are not limited to theses examples.

A halogen atom of 3-halogeno(alkyl)thietane can be converted to amercapto group by a substitution reaction. Known methods for thesubstitution reaction include a reaction using thiourea, a method usingan alkali metal hydrosulfide or alkali metal sulfide such as sodiumhydrosulfide, potassium hydrosulfide, sodium sulfide, potassium sulfide,or the like, a method using a metal polysulfide such as sodiumpolysulfide, potassium polysulfide, or the like, a method using analkali metal carbonate such as sodium trithiocarbonate, potassiumtrithiocarbonate, or the like, a method using potassium xanthogenate, amethod using a Bunte salt, and the like. In the method using athiocyanate, thiourea, triphenylphosphine sulfide, or the like,preferably a thiocyanate or thiourea, as a thianation agent,3-halogeno(alkyl)thietane is reacted with the thianation agent in atleast one solvent selected from water, an alcohol, a ketone, an ester,and the like to form an isothiuronium salt. The same alkali as describedabove is added to a solution containing the isothiuronium salt or theisolated isothiuronium salt and reacted therewith to synthesize3-mercapto(alkyl)thietane having a structure represented by formula(12).

(wherein R represents a substituted or unsubstituted divalenthydrocarbon group having 1 to 6 carbon atoms, and n represents aninteger of 0 to 3).

Preferred examples of the alkali used in the reaction include ammonia,sodium hydroxide, potassium hydroxide, calcium hydroxide, sodiumcarbonate, potassium carbonate, ammonium carbonate, and aqueoussolutions of these alkalis. Although the solvent used for adding thealkali depends upon the type of a compound to be synthesized, thesolvent need not be used, or any solvent may be used as long as it doesnot inhibit the reaction with the alkali and does not react with thealkali. Although the reaction temperature also depends upon the type ofthe compound to be synthesized, the reaction temperature of −30° C. to100° C. generally produces good results in some cases. The reactiontemperature is preferably −10° C. to 80° C., and more preferably 10° C.to 60° C.

3-mercapto(alkyl)thietane can be reacted with various halogenatedhydrocarbon compounds to synthesize the above-described various thietanecompounds. A method for reacting 3-mercapto(alkyl)thietane with ahalogenated hydrocarbon compound comprises adding a metal alkoxide to acomposition containing the halogenated hydrocarbon compound and3-mercapto(alkyl)thietane, and the method produces good results in somecases. Another method comprises reacting an alkali metal salt or metalalkoxide with 3-mercapto(alkyl)thietane to form a salt, and thusreacting the salt with the halogenated hydrocarbon compound, and themethod also produces good results in some cases. Although the reactionsolvent used in the methods depends upon the type of a compound to besynthesized, the solvent need not be used, or any solvent may be used aslong as it does not inhibit the reaction of the alkali metal salt ormetal alkoxide, 3-mercapto(alkyl)thietane and the halogenatedhydrocarbon compound and does not react with the alkali metal salt ormetal alkoxide. Although the reaction temperature also depends upon thetype of the compound to be synthesized, the reaction temperature of −70°C. to 50° C. generally produces good results in some cases, and thereaction temperature is preferably −50° C. to 50° C.

As the halogenated hydrocarbon compound used in the reaction, any one ofknown halogenated hydrocarbon compounds may be used. Preferred examplesof the halogenated hydrocarbon compound include aliphatic halogenatedhydrocarbon compounds such as 1,1-dichloromethane, 1,2-dichloroethane,1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane,1,4-dichlorobutane, 1,2,3-trichloropropane,tetrakis(chloromethyl)methane, 1,2-dichlorocyclohexane,bis(l-chloromethyl) sulfide, bis(2-chloroethyl) sulfide,2,3-dichloro-1-propanol, 1,1,1-trimethlychloroethane,1,1,1-trimethylchloropropane, 2,5-dichloromethylthiophane,4-chloromethyl-1,8-dichloro-3,6-dithiaoctane,2,5-dichloromethyl-1,4-dithiane,2,5-bis[(2-chloroethyl)thiomethyl]-1,4-dithiane,1,3-dichlorocyclohexane, 1,4-dichlorocyclohexane,4,8-dichloromethyl-1,11-chloro-3,6,9-trithiaundecane,4,7-dichloromethyl-1,11-chloro-3,6,9-trithiaundecane,5,7-dichloromethyl-1,11-chloro-3,6,9-trithiaundecane, and the like, andcompounds in which chloro groups of these compounds are substituted bybromo or iodo groups; aromatic halogenated hydrocarbon compounds such as1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene,1,2-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene,1,4-bis(chloromethyl)benzene, 2,2′-dichlorobiphenyl,4,4′-dichlorobiphenyl, bis(4-chlorophenyl)methane, bis(4-chlorophenyl)sulfide, bis(4-chlorophenyl) sulfone, 2,2-bis(4-chlorophenyl)propane,1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,5-trichlorobenzene,and the like, and compounds having bromo or iodo groups substituted forthe chloro groups of these compounds. However, the halogenatedhydrocarbon compounds are not limited to these examples.

Also, a compound having another functional group which can react with amercapto group, for example, an aldehyde, an acetal, a ketone, a ketal,an epoxy, an episulfide, an olefin, an iso(thio)cyanate, a thiol, anacid halide, an acid anhydride, or the like, may be reacted with a3-mercapto(alkyl)thietane compound to directly synthesize a compoundhaving the structure represented by formula (4) in which the reactiveterminal group is a thietanyl group. Examples of aldehydes, acetals andketones include aldehydes such as formaldehyde, acetoaldehyde,propionaldehyde, benzaldehyde, glyoxal, malonaldehyde,2-thiophenaldehyde, methylbenzaldehyde, phthalaldehyde, and the like;acetal compounds of these aldehyde compounds; ketones such as acetone,acetophenone, benzophenone, methyl ethyl ketone, cyclopentanone,cyclohexanedione, and the like; ketals of these ketones; and the like.Examples of epoxys, episulfides, olefins, iso(thio)cyanates, thiols,acid halides, and acid anhydrides include the compounds havingfunctional groups, which are described above and below. However, thecompounds are not limited to these examples.

Furthermore, a thietane compound having a disulfide bond can besynthesized by inter-molecular oxidation of the3-mercapto(alkyl)thietane compound. Therefore, bis(3-thietanyl)disulfide can be synthesized by oxidation of the 3-mercaptothietane.Similarly, bis(3-thietanylalkyl) disulfide can be synthesized by using a3-mercapto(alkyl)thietane compound. As the oxidizing agent used for theoxidation reaction, any oxidizing agent usually used for oxidizing amercapto group to form a disulfide bond may be used. Examples of theoxidizing agent include oxygen, hydrogen peroxide and an aqueoussolution thereof, hypohalogenous acid salts such as sodium hypochlorite,and the like, and aqueous solutions of these salts; persulfates such asammonium persulfate, and the like, aqueous solutions of thesepersulfates; halogens such as iodine, bromine, chlorine, and the like;sulfuryl chloride; iron (III) chloride; sulfoxide compounds such asdimethylsulfoxide, and the like; nitrogen oxide; and the like. However,the oxidizing agents are not limited to these compound examples.Although the reaction solvent used in the oxidation reaction dependsupon the type of the compound to be synthesized, the solvent need not beused, or any solvent may be used as long as it does not inhibit theeffect of the oxidizing agent and does not react with the oxidizingagent. Although the reaction temperature also depends upon the type ofthe compound to be synthesized, the reaction temperature of −70° C. to100° C. usually produces good results in some cases, and the reactiontemperature is preferably −30° C. to 80° C.

In an example of a method for synthesizing a compound having thestructure represented by formula (1) having an oxetanyl terminal group,a compound having a structure represented by formula (13) in which theterminal group in the structure represented by formula (1) is a mercaptogroup is mixed with 3-halogeno(alkyl)oxetane, and a metal alkoxide isadded to the resultant mixture to produce good results in some cases.

(wherein Q′ represents a hydrogen atom or a straight, branched or cyclicalkyl group having 1 to 10 carbon atoms and at least a mercapto group orits thia derivative, an aryl group, or an aralkyl group, R″″ representsa substituted or unsubstituted straight, branched or cyclic hydrocarbongroup having 1 to 6 carbon atoms, and n represents an integer of 0 to3.)

Also, an alkali metal salt or metal alkoxide may be reacted with acompound having the structure represented by formula (13) to form asalt, and then the salt is reacted with 3-halogeno(alkyl)oxetane toproduce good results in some cases. Although the reaction solvent usedin the reaction depends upon the type of the compound to be synthesized,the solvent need not be used, or any solvent may be used as long as itdoes not inhibit the reaction of the alkali metal salt or metalalkoxide, the compound having the structure represented by formula (13)and the halogenated hydrocarbon compound, and does not react with thealkali metal salt or metal alkoxide. Although the reaction temperaturealso depends upon the type of the compound to be synthesized, thereaction temperature of −70° C. to 50° C. usually produces good resultsin some cases, and the reaction temperature is preferably −50° C. to 50°C.

As the 3-halogeno(alkyl)oxetane compound used in this method, any known3-halogeno(alkyl)oxetane compound or a 3-halogeno(alkyl)oxetane compoundobtained by halogenating a 3-hydroxy(alkyl)oxetane compound may be used.Preferred examples of the oxetane compound include3-chloro(alkyl)oxetane compounds such as 3-chloromethyloxetane,3-chloroethyloxetane, and the like; 3-chloro(alkyl)-3-(alkyl)oxetanecompounds such as 3-chloromethyl-3-methyloxetane,3-chloromethyl-3-ethyloxetane, 3-chloroethyl-3-ethyloxetane, and thelike. However, the oxetane compounds are not limited to these examples.

Preferred examples of the compound having the structure represented byformula (13) include aliphatic compounds such as3-(mercaptomethylthio)thietane, 3-(mercaptoethylthio)thietane,3-(1-mercaptopropyl-2-thio)thietane,3-(1-mercaptopropyl-3-thio)thietane,3-(2-mercaptopropyl-2-thio)thietane, 3-(1-mercaptobutyl-4-thio)thietane,3-(mercaptomethylthiomethylthio)thietane,3-(mercaptoethylthioethylthio)thietane,3-(2-mercapto-1-hydroxypropyl-3-thio)thietane,3-(3-mercapto-2-hydroxypropyl-1-thio)thietane,3-(2-mercaptomethylthiophene-5-methylthio)thietane,3-(2-mercaptomethyl-1,4-dithiane-5-methylthio)thietane,3-(1-mercaptocyclohexane-2-thio)thietane,3-(1-mercaptocyclohexane-3-thio)thietane,3-(1-mercaptocyclohexane-4-thio)thietane, and the like; aromaticcompounds such as 3-(1-mercaptobenzene-2-thio)thietane,3-(1-mercaptobenzene-3-thio)thietane,3-(1-mercaptobenzene-4-thio)thietane,3-(1-mercaptomethylbenzene-2-methylthio)thietane,3-(1-mercaptomethylbenzene-3-methylthio)thietane,3-(1-mercaptomethylbenzene-4-methylthio)thietane, and the like. However,the compounds are not limited to these examples.

In an example of a method for synthesizing a compound having thestructure represented by formula (1) having an epoxy and/or episulfidoterminal group, 3-mercapto(alkyl)thietane is reacted with epihalohydrinin the presence of an alkali catalyst to synthesize(3-chloro-2-hydroxypropanylthio) (alkyl)thietane as a halohydrincompound, and then the halohydrin compound is dehydrochlorinated with analkali to obtain 3-(2,3-epoxypropylthio)(alkyl)thietane. As the alkaliused, either an inorganic alkali or organic alkali may be used, and analkali metal or alkali earth metal hydroxide, an alkali metal or alkaliearth metal carbonate, an alkali metal or alkali earth metalbicarbonate, ammonia, a tertiary amine, a secondary amine, a primaryamine, a metal alkoxide, or the like is preferably used. Although thesolvent used for adding the alkali depends upon the type of the compoundto be synthesized, the solvent need not be used, or any solvent may beused as long as it does not inhibit the reaction with the alkali anddoes not react with the alkali. Although the reaction temperature alsodepends upon the type of the compound to be synthesized, the reactiontemperature of −30° C. to 100° C. usually produces good results in somecases. The reaction temperature is preferably −10° C. to 80° C., andmore preferably 10° C. to 60° C. In another method, a3-hydroxy(alkyl)thietane compound is condensed with1-chloro-3-mercaptopropane-2-ol in the presence of an acid catalyst tosynthesize (3-chloro-2-hydroxypropylthio) (alkyl)thietane as ahalohydrin compound, and then the halohydrin compound isdehydrochlorinated with an alkali in the same manner as described above.Although the solvent used for condensation depends upon the type of acompound to be synthesized, the solvent need not be used, or any solventmay be used as long as it does not inhibit the condensation, and asolvent which permits azeotropic dehydration is preferably used forincreasing the reaction efficiency. Although the reaction temperaturealso depends upon the type of the compound to be synthesized, thereaction temperature of 0° C. to 120° C. usually produces good resultsin some cases, and the reaction temperature is preferably 20° C. to 110°C., and more preferably 30° C. to 90° C.

Preferred examples of the resultant 3-(2,3-epoxypropylthio)(alkyl)thietane compound include aliphatic compounds such as3-(2,3-epoxypropylthio)thietane, 3-(2,3-epoxypropyldithio)thietane,3-(2,3-epoxypropylthiomethyl)thietane,3-(2,3-epoxypropylthioethylthio)thietane,3-(2,3-epoxypropylthiopropylthio)thietane,3-(2,3-epoxypropylthiobutylthio)thietane,3-(2,3-epoxypropylthiomethylthiometylthio)thietane,3-(2,3-epoxypropylthioethylthioethylthio)thietane,3-(2,3-epoxypropylthiohydroxypropylthio)thietane,3-[2-(2,3-epoxypropylthio)methylthiophene-5-methylthio]thietane,3-[2-(2,3-epoxypropylthio)methyl-1,4-dithiane-5-methylthio]thietane,3-[1-(2,3-epoxypropylthio)cyclohexane-2-thia]thietane,3-[1-(2,3-epoxypropylthio)cyclohexane-3-thia]thietane,3-[1-(2,3-epoxypropylthio)cyclohexane-4-thia]thietane, and the like;aromatic compounds such as3-[1-(2,3-epoxypropylthio)benzene-2-thia]thietane,3-[1-(2,3-epoxypropylthio)benzene-3-thia]thietane,3-[1-(2,3-epoxypropylthio)benzene-4-thia]thietane,3-[1-(2,3-epoxypropylthio)methylbenzene-2-methylthio]thietane,3-[1-(2,3-epoxypropylthio)methylbenzene-3-methylthio]thietane,3-[1-(2,3-epoxypropylthio)methylbenzene-4-methylthio]thietane, and thelike. However, the thietane compounds are not limited to these examples.

The resultant compound having the structure represented by formula (1)having an epoxy terminal group may be reacted with a thianation agent tosynthesize a compound having a structure represented by formula (1)having an episulfido terminal group. As the thianation agent, athiocyanate, thiourea, triphenylphosphine sulfide, or the like,preferably, a thiocyanate or thiourea, is used. The compound may besynthesized by a reaction, if required, in a catalytic amount of atleast one polar solvent selected from organic acids such as formic acid,acetic acid, propionic acid, phthalic acid, and the like, halogenatedproducts anhydrides thereof, inorganic acids such as hydrochloric acid,sulfuric acid, nitric acid, phosphoric acid, and the like, water,alcohols, ketones, ethers, and esters, and if required, a known organicsolvent which can dissolve the resultant episulfide compound are usedfor obtaining the episulfide compound. The reaction may be effected inat least one polar solvent in an amount substantially equivalent tothiourea to form an isothiuronium salt, the polar solvent being selectedfrom organic acids such as formic acid, acetic acid, propionic acid,phthalic acid, and the like, halogenated products and anhydrides ofthese organic acids, inorganic acids such as hydrochloric acid, sulfuricacid, nitric acid, phosphoric acid, and the like, water, alcohols,ketones, ethers, and esters. Then, the same alkali as described abovemay be added to a solution containing the isothiuronium salt or theisolated isothiuronium salt and reacted with the isothiuronium salt tosynthesize the episulfide compound. Preferred examples of the alkaliinclude ammonia, sodium hydroxide, potassium hydroxide, calciumhydroxide, sodium carbonate, potassium carbonate, and ammoniumcarbonate, and aqueous solutions of these alkalis. Although the solventused for adding the alkali depends upon the type of a compound to besynthesized, the solvent need not be used, or any solvent may be used aslong as it does not inhibit the reaction with the alkali and does notreact with the alkali. Although the reaction temperature also dependsupon the type of the compound to be synthesized, the reactiontemperature of −30° C. to 100° C. usually produces good results in somecases, and the reaction temperature is preferably −10° C. to 80° C., andmore preferably 10° C. to 60° C.

Preferred examples of the thietane compound having the structurerepresented by formula (1) in which the terminal group is an episulfidegroup include aliphatic compounds such as3-(2,3-epithiopropylthio)thietane, 3-(2,3-epithiopropyldithio)thietane,3-(2,3-epithiopropylthiomethyl)thietane,3-(2,3-epithiopropylthioethylthio)thietane,3-(2,3-epithiopropylthiopropylthio)thietane,3-(2,3-epithiopropylthiobutylthio)thietane,3-(2,3-epithiopropylthiomethylthiomethylthio)thietane,3-(2,3-epithiopropylthioethylthioethylthio)thietane,3-(2,3-epithiopropylthiohydroxypropylthio)thietane,3-[2-(2,3-epithiopropylthio)methylthiophene-5-methylthio]thietane,3-[2-(2,3-epithiopropylthio)methyl-1,4-dithiane-5-methylthio]thietane,3-[1-(2,3-epithiopropylthio)cyclohexane-2-thio]thietane,3-[1-(2,3-epithiopropylthio)cyclohexane-3-thio]thietane,3-[1-(2,3-epithiopropylthio)cyclohexane-4-thio]thietane, and the like;aromatic compounds such as3-[1-(2,3-epithiopropylthio)benzene-2-thia]thietane,3-[1-(2,3-epithiopropylthio)benzene-3-thia]thietane,3-[1-(2,3-epithiopropylthio)benzene-4-thia]thietane,3-[1-(2,3-epithiopropylthio)methylbenzene-2-methylthio]thietane,3-[1-(2,3-epithiopropylthio)methylbenzene-3-methylthio]thietane,3-[1-(2,3-epithiopropylthio)methylbenzene-4-methylthio]thietane, and thelike. However, the thietane compounds are not limited to these examples.

A method for synthesizing a compound having the structure represented byformula (1) in which the terminal group is an amino group, an isocyanatogroup, an isothiocyanato(meth)acryl group, an allyl group, a vinylgroup, or an isopropenyl group is the following general method.

A compound having an amino group is synthesized by a known alkyl halideamination method for aminating a thietane compound having a halogenoterminal group. For example, an alkali metal azide compound is reactedwith an alkyl halide to synthesize an azide compound, and then the azidecompound is converted to an amino compound by a Bechamp reductionprocess, a process using lithium aluminum hydride or sodium boronhydride and iodine, or a process using hydrogen in the presence of anAdams catalyst. The amino compound can also be synthesized by anammonolysis process, a Gabriel's process, a Delepine process, a hexamineprocess, or the like in some cases. Also, the target compound can easilybe synthesized by reacting the thietane compound having a hydroxyl groupand/or mercapto group at the terminal with halogenoalkylamine (or itssalt such as hydrochloride or the like) in the presence of an alkali.

A compound having an isocyanato group can be synthesized by reacting theamino compound with phosgene. The reaction with phosgene is effected bya cold-hot two-step method comprising reacting an amine with phosgene ata low temperature and then reacting the reaction product with phosgeneat a high temperature, a hydrochloride method comprising forming ahydrochloride using an amine and hydrochloric acid gas, and then thehydrochloride with phosgene, or the like. The compound can also besynthesized by reacting a halogenated acid ester such as chloroacetateester or the like with the thietane compound having a hydroxyl groupand/or mercapto group at the terminal to form a hydrazide compound usinghydrazine, and then reacting the hydrazide compound with nitrous acid toproduce a Curtius rearrangement reaction through an acid azide compound.

A compound having an isothiocyanato group can be synthesized by a methodin which the amino compound is reacted with carbon disulfide and analkali such as caustic soda or the like, and then the reaction productis decomposed with a chlorinating agent such as alkyl chloroformate orthe like. Also, a method of reacting thiophosgene with the aminocompound is preferably used.

A compound having a (meth)acryl group is synthesized by a method inwhich a halogenated acid halide such as chloropropionyl chloride or thelike is reacted with the thietane compound having a hydroxyl groupand/or mercapto group at the terminal, and then the reaction product isdehydrohalogenated with an alkali such as a tertiary amine or alkalimetal salt or its aqueous solution, a metal alkoxide, or the like, or amethod in which the thietane compound is reacted directly with an acidchloride such as (meth)acrylic chloride or the like.

A compound having an ally group, a vinyl group, or an isopropenyl groupis synthesized by a method in which the thietane compound having ahydroxy group and/or mercapto group at the terminal is reacted with anally halide such as allyl chloride or the like, a vinyl halide such asvinyl bromide or the like, or isopropenyl halide such as isopropenylchloride or the like in the presence of the alkali. The methods forsynthesizing the compounds having the structures represented by formula(1) having an amino terminal group, an isocyanato terminal group, anisothiocyanato terminal group, a (meth)acryl terminal group, an allylterminal group, a vinyl terminal group, and an isopropenyl terminalgroup, respectively, depends upon the structures of the target compoundsand are not limited to the above-described methods. The used solvent andreaction temperature also depend upon the target compounds and are notlimited. Preferred examples of these compounds having the structuresrepresented by formula (1) having an amino terminal group, an isocyanatoterminal group, a (meth)acryl terminal group, an allyl terminal group, avinyl terminal group, and an isopropenyl terminal group, respectively,include 3-(aminomethylthio)thietane, 3-[iso(thio)cyanatothio]thietane,3-(aminoethylthio)thietane, 3-[iso(thio)cyanatoethylthio]thietane,3-[(meth)acryloylthio]thietane, 3-(allylthio)thietane,3-(vinylthio)thietane, 3-(isopropenylthio)thietane, and the like. Thecompounds are not limited to these examples.

Besides the above-described 3-thietanyl compounds, 2-thietanyl compoundscan be synthesized in the same manner as the 3-thietanyl compounds. Morespecifically, 3,3-dimercapto-1-halogenopropane is reacted with3,3-dialkyloxy-1-halogenoproane (for example, 3-chloropropionaldehydediethylacetal) and hydrogen sulfide. The resultant3,3-dimercapto-1-halogenoproane is reacted with the same alkali asdescribed above in the presence or absence of a solvent to synthesize2-mercaptoethietane through intramolecular cyclization. Thethus-obtained 2-mercaotpthietane can be subjected to the above-describedvarious reactions to synthesize compounds having various structuresderived from a 2-thietanyl group.

A polymerizable composition containing the sulfur-containing cyclicompound having the structure represented by formula (1) of the presentinvention comprises at least one sulfur-containing cyclic compoundhaving the structure represented by formula (1). However, in some cases,in order to obtain a good resin, a method or operation generally usedfor synthesizing an organic compound, such as purification, cleaning,hot insulation, cold insulation, filtration, reduced-pressure treatment,or the like is preferably performed, or a known compound is preferablyadded as a stabilizer or resin modifier for improving a resin andhandleability, for example, for controlling the optical physicalproperties such as the refractive index and Abbe's number, and the like,physical properties such as a hue, light resistance, weather resistance,heat resistance, impact resistance, hardness, specific gravity, linearexpansion coefficient, polymerization shrinkability, water absorption,hygroscopicity, chemical resistance, viscoelasticity, and the like, andtransmittance and transparency of a resin produced by curing thepolymerizable composition, and controlling the viscosity of thepolymerizable composition, and preservation and transport handleability.Examples of compounds added for improving stability such as long-termpreservation stability, polymerization stability and thermal stabilityinclude a polymerization retardant, a polymerization inhibitor, adeoxidant, an antioxidant, and the like. However, the compounds are notlimited to these examples.

Purification of the polymerizable composition is a means for improvingthe transparency of the resin produced by curing, or increasing thepurity of the resin to improving the hue thereof. As a method forpurifying the polymerizable composition containing the sulfur-containingcyclic compound having the structure represented by formula (1) of thepresent invention, any known method, for example, distillation,recrystallization, column chromatography (a silica gel method, anactivated carbon method, an ion-exchange resin method, or the like),extraction, or the like, may be performed with any timing as long as thetransparency and hue of the resin obtained by curing the purifiedcomposition are improved.

As a method for cleaning the polymerizable composition, a method forimproving the transparency and hue of the resin obtained by curing maybe used with timing when or after the synthesized polymerizablecomposition is taken out. In this method, the composition is washed witha polar and/or nonpolar solvent to remove or reduce a resin transparencyinhibitor, for example, an inorganic salt used for synthesizing thepolymerizable composition or secondarily produced in synthesizing thecomposition, such as an ammonium salt, thiourea, or the like. Althoughthe solvent used depends upon the polymerizable composition to becleaned and the polarity of a solution containing the polymerizablecomposition, and is not limited, a solvent which can dissolve acomponent to be removed, and which is incompatible with thepolymerizable composition to be cleaned and the solution containing thepolymerizable composition is preferably used. The solvent may be usedsingly, or a mixture of at least two solvents may be used. Although theamount of a component to be removed depends upon the purpose andapplication, the amount is preferably as low as possible. The amount ispreferably 5000 ppm or less, more preferably 1000 ppm or less, and mostpreferably 100 ppm or less.

As a hot insulation, cold insulation or filtration method for thepolymerizable composition, a method for improving the transparency andhue of the resin obtained by curing is generally used with timing whenor after the synthesized polymerizable composition is taken out. In thehot insulation method, for example, when the polymerizable compositionis crystallized to deteriorate handleability during storage, thepolymerizable composition is melted by heating within a range causing nodeterioration in the performance of the polymerizable composition andthe resin obtained by curing the polymerizable composition. Although theheating temperature range and heat melting method depend upon thecompound constituting the polymerizable composition to be handled andare not limited, the heating temperature is generally in a range of thesolidification point+50° C., and preferably the solidification point+20°C. In this method, the composition may be melted by mechanicallystirring with a stirring device or bubbling with an inert gas for movingan internal liquid. The cold insulation method is generally performedfor improving the preservation stability of the polymerizablecomposition. However, when the composition has a high melting point andthus has a problem about handleability after crystallization,consideration must be given to the storage temperature. Although thecold insulation temperature depends upon the structure and preservationstability of the compound constituting the polymerizable composition tobe handled and is not limited, the polymerizable composition containinga compound having the structure represented by formula (1) is preferablystored at a low temperature of 20° C. or less, and more preferably 10°C. or less. However, when the composition has a high melting point,storage at a temperature higher than the solidification temperaturegenerally improves handleability in some cases of use. When heat-meltingcan easily be performed, storage at a temperature lower than thesolidification temperature has no problem.

The polymerizable composition used for optical applications is requiredto have high transparency, and thus the polymerizable composition ispreferably filtered with a filter having a small pore size. Although thepore size of the filter used is usually 0.05 to 10 μm, the pore size ispreferably 0.05 to 5 μm, and more preferably 0.1 to 5 μm, from theviewpoint of operationality and performance. In many cases, filtrationof the polymerizable composition containing the sulfur-containing cycliccompound of the present invention produces good results withoutexception. Although a low filtration temperature near the solidificationtemperature produces more desirable results in some cases, filtration ispreferably performed at a temperature causing no trouble in thefiltration work when solidification proceeds during filtration.

The reduced-pressure treatment is a means for removing a solvent,dissolved gas and odor which deteriorate the performance of the resingenerally produced by curing the polymerizable composition. Since adissolved solvent generally decreases the refractive index of theresultant resin and deteriorates the heat resistance thereof, thedissolved solvent must be removed as much as possible. Although theallowable amount of the dissolved solvent depends upon the structure ofthe compound constituting the polymerizable composition to be handledand the structure of the dissolved solvent and is not limited, theallowable amount is usually 1% or less, and preferably 5000 ppm or less.The dissolved gas inhibits polymerization or causes the problem ofmixing bubbles in the resultant resin, and is thus preferably removed.Particularly, a moisture gas such as water vapor or the like ispreferably removed by bubbling with a dry gas. The amount of thedissolved gas depends upon the structure of the compound constitutingthe polymerizable composition, the physical properties, structure andtype of the dissolved gas and is not limited.

Examples of the resin modifier include known thietane compounds otherthan the thietane compound contained in the polymerizable composition ofthe present invention, dithietane compounds, trithietane compounds,thiolane compounds, dithiolane compounds, trithiolane compounds,dithiane compounds, trithiane compounds, episulfide compounds, epoxycompounds, amine compounds, thiol compounds, hydroxyl compoundsincluding phenol compounds, iso(thio)cyanato compounds, mercapto organicacids, organic acids, anhydrides, amino acids, mercapto amines, olefinsincluding (meth)acrylates, cyclic organic and inorganic compounds eachhaving a sulfur atom or selenium atom, and the like. Of these resinmodifiers, epoxy compounds, iso(thio)cyanato compounds, olefinsincluding (meth)acrylates are preferred for overcoming brittleness ofthe resultant resin and for improving the impact resistance thereof.Also, amine compounds, thiol compounds, and phenol compounds arepreferred for improving the hue of the resultant resin. Particularly, acompound having at least one SH group and/or a NH group and/or a NH₂group is more preferred.

Examples of an episulfide compound used as the resin modifier in thepresent invention include epithioethyl compounds such asbis(1,2-epithioethyl) sulfide, bis(1,2-epithioethyl) disulfide,bis(epithioethylthio)methane, bis(epithioethylthio)benzene,bis[4-(epithioethylthio)phenyl] sulfide,bis[4-(epithioethylthio)phenyl]methane, and the like; chain aliphatic2,3-epithiopropylthio compounds such as bis(2,3-epithiopropyl) sulfide,bis(2,3-epithiopropyl) disulfide, bis(2,3-epithiopropylthio)methane,1,2-bis(2,3-epithiopropylthio)ethane,1,2-bis(2,3-epithiopropylthio)propane,1,3-bis(2,3-epithiopropylthio)propane,1,3-bis(2,3-epithiopropylthio)-2-methylpropane,1,4-bis(2,3-epithiopropylthio)butane,1,4-bis(2,3-epithiopropylthio)-2-methylbutane,1,3-bis(2,3-epithiopropylthio)butane,1,5-bis(2,3-epithiopropylthio)pentane,1,5-bis(2,3-epithiopropylthio)-2-methylpentane,1,5-bis(2,3-epithiopropylthio)-3-thiapentane,1,6-bis(2,3-epithiopropylthio)hexane,1,6-bis(2,3-epithiopropylthio)-2-methylhexane,3,8-bis(2,3-epithiopropylthio)-3,6-dithiaoctane,1,2,3-tris(2,3-epithiopropylthio)propane,2,2-bis(2,3-epithiopropylthio)-1,3-bis(2,3-epithiopropylthiomethyl)propane,2,2-bis(2,3-epithiopropylthiomethyl)-1-(2,3-epithiopropylthio)butane,1,5-bis(2,3-epithiopropylthio)-2-(2,3-epithiopropylthiomethyl)-3-thiapentane,1,5-bis(2,3-epithiopropylthio)-2,4-bis(2,3-epithiopropylthiomethyl)-3-thiapentane,1-(2,3-epithiopropylthio)-2,2-bis(2,3-epithiopropylthiomethyl)-4-thiahexane,1,5,6-tris(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl)-3-thiahexane,1,8-bis(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-4,5-bis(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-4,4-bis(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-2,5-bis(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-2,4,5-tris(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,1,1-tris[[2-(2,3-epithiopropylthio)ethyl]thiomethyl]-2-(2,3-epithiopropylthio)ethane,1,1,2,2-tetrakis[[2-(2,3-epithiopropylthio)ethyl]thiomethyl]ethane,1,11-bis(2,3-epithiopropylthio)-4,8-bis(2,3-epithiopropylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epithiopropylthio)-4,7-bis(2,3-epithiopropylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epithiopropylthio)-5,7-bis(2,3-epithiopropylthiomethyl)-3,6,9-trithiaundecane,and the like; alicyclic 2,3-epithiopropylthio compounds such as1,3-bis(2,3-epithiopropylthio)cyclohexane,1,4-bis(2,3-epithiopropylthio)cyclohexane,1,3-bis(2,3-epithiopropylthiomethyl)cyclohexane,1,4-bis(2,3-epithiopropylthiomethyl)cyclohexane,2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane,2,5-bis[[2-(2,3-epithiopropylthio)ethyl]thiomethyl]-1,4-dithiane,2,5-bis(2,3-epithiopropylthiomethyl)-2,5-dimethyl-1,4-dithiane, and thelike; aromatic 2,3-epithiopropylthio compounds such as1,2-bis(2,3-epithiopropylthio)benzene,1,3-bis(2,3-epithiopropylthio)benzene,1,4-bis(2,3-epithiopropylthio)benzene,1,2-bis(2,3-epithiopropylthiomethyl)benzene,1,3-bis(2,3-epithiopropylthiomethyl)benzene,1,4-bis(2,3-epithiopropylthiomethyl)benzene,bis[4-(2,3-epithiopropylthio)phenyl]methane,2,2-bis[4-(2,3-epithiopropylthio)phenyl]propane,bis[4-(2,3-epithiopropylthio)phenyl] sulfide,bis[4-(2,3-epithiopropylthio)phenyl] sulfone,4,4′-bis(2,3-epithiopropylthio)biphenyl, and the like; monofunctionalepisulfide compounds such as ethylene sulfide, propylene sulfide,mercaptopropylene sulfide, mercaptobutene sulfide, epithiochlorohydrin,and the like; chain aliphatic 2,3-epithiopropyloxy compounds such asbis(2,3-epithiopropyl) ether, bis(2,3-epithiopropyloxy)methane,1,2-bis(2,3-epithiopropyloxy)ethane,1,2-bis(2,3-epithiopropyloxy)propane,1,3-bis(2,3-epithiopropyloxy)propane,1,3-bis(2,3-epithiopropyloxy)-2-methylpropane,1,4-bis(2,3-epithiopropyloxy)butane,1,4-bis(2,3-epithiopropyloxy)-2-methylbutane,1,3-bis(2,3-epithiopropyloxy)butane,1,5-bis(2,3-epithiopropyloxy)pentane,1,5-bis(2,3-epithiopropyloxy)-2-methylpentane,1,5-bis(2,3-epithiopropyloxy)-3-thiapentane,1,6-bis(2,3-epithiopropyloxy)hexane,1,6-bis(2,3-epithiopropyloxy)-2-methylhexane,3,8-bis(2,3-epithiopropyloxy)-3,6-dithiaoctane,1,2,3-tris(2,3-epithiopropyloxy)propane,2,2-bis(2,3-epithiopropyloxy)-1,3-bis(2,3-epithiopropyloxymethyl)propane,2,2-bis(2,3-epithiopropyloxymethyl)-1-(2,3-epithiopropyloxy)butane,1,5-bis(2,3-epithiopropyloxy)-2-(2,3-epithiopropyloxymethyl)-3-thiapentane,1,5-bis(2,3-epithiopropyloxy)-2,4-bis(2,3-epithiopropyloxymethyl)-3-thiapentane,1-(2,3-epithiopropyloxy)-2,2-bis(2,3-epithiopropyloxymethyl)-4-thiahexane,1,5,6-tris(2,3-epithiopropyloxy)-4-(2,3-epithiopropyloxymethyl)-3-thiahexane,1,8-bis(2,3-epithiopropyloxy)-4-(2,3-epithiopropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropyloxy)-4,5-bis(2,3-epithiopropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropyloxy)-4,4-bis(2,3-epithiopropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropyloxy)-2,5-bis(2,3-epithiopropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropyloxy)-2,4,5-tris(2,3-epithiopropyloxymethyl)-3,6-dithiaoctane,1,1,1-tris[[2-(2,3-epithiopropyloxy)ethyl]thiomethyl]-2-(2,3-epithiopropyloxy)ethane,1,1,2,2-tetrakis[[2-(2,3-epithiopropyloxy)ethyl]thiomethyl]ethane,1,11-bis(2,3-epithiopropyloxy)-4,8-bis(2,3-epithiopropyloxymethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epithiopropyloxy)-4,7-bis(2,3-epithiopropyloxymethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epithiopropyloxy)-5,7-bis(2,3-epithiopropyloxymethyl)-3,6,9-trithiaundecane,and the like; alicyclic 2,3-epithiopropyloxy compounds such as1,3-bis(2,3-epithiopropyloxy)cyclohexane,1,4-bis(2,3-epithiopropyloxy)cyclohexane,1,3-bis(2,3-epithiopropyloxymethyl)cyclohexane,1,4-bis(2,3-epithiopropyloxymethyl)cyclohexane,2,5-bis(2,3-epithiopropyloxymethyl)-1,4-dithiane,2,5-bis[[2-(2,3-epithiopropyloxy)ethyl]thiomethyl]-1,4-dithiane,2,5-bis(2,3-epithiopropyloxymethyl)-2,5-dimethyl-1,4-dithiane, and thelike; aromatic 2,3-epithiopropyloxy compounds such as1,2-bis(2,3-epithiopropyloxy)benzene,1,3-bis(2,3-epithiopropyloxy)benzene,1,4-bis(2,3-epithiopropyloxy)benzene,1,2-bis(2,3-epithiopropyloxymethyl)benzene,1,3-bis(2,3-epithiopropyloxymethyl)benzene,1,4-bis(2,3-epithiopropyloxymethyl)benzene,bis[4-(2,3-epithiopropyloxy)phenyl]methane,2,2-bis[4-(2,3-epithiopropyloxy)phenyl]propane,bis[4-(2,3-epithiopropyloxy)phenyl] sulfide,bis[4-(2,3-epithiopropyloxy)phenyl] sulfone,4,4′-bis(2,3-epithiopropyloxy)biphenyl, and the like. However, theepisulfide compounds are not limited to these examples.

Of these compound examples, bis(1,2-epithioethyl) sulfide,bis(1,2-epithioethyl) disulfide, bis(2,3-epithiopropyl) disulfide,bis(2,3-epithiopropylthio)methane and bis(2,3-epithiopropyl) disulfideare preferred, and bis(1,2-epithioethyl) sulfide, bis(1,2-epithioethyl)disulfide, and bis(2,3-epithiopropyl) disulfide are more preferred.

Examples of an epoxy compound used as the resin modifier in the presentinvention include phenolic epoxy compounds each obtained by acondensation reaction of an epihalohydrin compound and a polyhydricphenol compound such as bisphenol A glycidyl ether or the like,alcoholic epoxy compounds each obtained by condensation of anepihalohydrin compound and a polyhydric alcohol compound such ashydrogenated bisphenol A glycidyl ether or the like, glycidyl ester-typeepoxy compounds each obtained by condensation of an epihalohydrincompound and a polyvalent organic acid compound such as3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, diglycidyl1,2-hexahydrophthalate, or the like, amine-type epoxy compounds eachobtained by condensation of a secondary amine compound and anepihalohydrin compound, aliphatic polyvalent epoxy compounds such asvinylcyclohexene diepoxide, and the like.

Examples of sulfide group-containing epoxide compounds and ethergroup-containing epoxide compounds include chain aliphatic2,3-epoxypropylthio compounds such as bis(2,3-epoxypropyl) sulfide,bis(2,3-epoxypropyl) disulfide, bis(2,3-epoxypropylthio)methane,1,2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane,1,3-bis(2,3-epoxypropylthio)propane,1,3-bis(2,3-epoxypropylthio)-2-methylpropane,1,4-bis(2,3-epoxypropylthio)butane,1,4-bis(2,3-epoxypropylthio)-2-methylbutane,1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,3-epoxypropylthio)pentane,1,5-bis(2,3-epoxypropylthio)-2-methylpentane,1,5-bis(2,3-epoxypropylthio)-3-thiapentane,1,6-bis(2,3-epoxypropylthio)hexane,1,6-bis(2,3-epoxypropylthio)-2-methylhexane,3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane,1,2,3-tris(2,3-epoxypropylthio)propane,2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthiomethyl)propane,2,2-bis(2,3-epoxypropylthiomethyl)-1-(2,3-epoxypropylthio)butane,1,5-bis(2,3-epoxypropylthio)-2-(2,3-epoxypropylthiomethyl)-3-thiapentane,1,5-bis(2,3-epoxypropylthio)-2,4-bis(2,3-epoxypropylthiomethyl)-3-thiapentane,1-(2,3-epoxypropylthio)-2,2-bis(2,3-epoxypropylthiomethyl)-4-thiahexane,1,5,6-tris(2,3-epoxypropylthio)-4-(2,3-epoxypropylthiomethyl)-3-thiahexane,1,8-bis(2,3-epoxypropylthio)-4-(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropylthio)-4,5-bis(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropylthio)-4,4-bis(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropylthio)-2,5-bis(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropylthio)-2,4,5-tris(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane,1,1,1-tris[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]-2-(2,3-epoxypropylthio)ethane,1,1,2,2-tetrakis[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]ethane,1,11-bis(2,3-epoxypropylthio)-4,8-bis(2,3-epoxypropylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epoxypropylthio)-4,7-bis(2,3-epoxypropylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epoxypropylthio)-5,7-bis(2,3-epoxypropylthiomethyl)-3,6,9-trithiaundecane,and the like; alicyclic 2,3-epoxypropylthio compounds such as1,3-bis(2,3-epoxypropylthio)cyclohexane,1,4-bis(2,3-epoxypropylthio)cyclohexane,1,3-bis(2,3-epoxypropylthiomethyl)cyclohexane,1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane,2,5-bis(2,3-epoxypropylthiomethyl)-1,4-dithiane,2,5-bis[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]-1,4-dithiane,2,5-bis(2,3-epoxypropylthiomethyl)-2,5-dimethyl-1,4-dithiane, and thelike; aromatic 2,3-epoxypropylthio compounds such as1,2-bis(2,3-epoxypropylthio)benzene,1,3-bis(2,3-epoxypropylthio)benzene,1,4-bis(2,3-epoxypropylthio)benzene,1,2-bis(2,3-epoxypropylthiomethyl)benzene,1,3-bis(2,3-epoxypropylthiomethyl)benzene,1,4-bis(2,3-epoxypropylthiomethyl)benzene,bis[4-(2,3-epoxypropylthio)phenyl]methane,2,2,-bis[4-(2,3-epoxypropylthio)phenyl]propane,bis[4-(2,3-epoxypropylthio)phenyl] sulfide,bis[4-(2,3-epoxypropylthio)phenyl] sulfone,4,4′-bis(2,3-epoxypropylthio)biphenyl, and the like; monofunctionalepoxy compounds such as ethylene oxide, propylene oxide, glycidol,epichlorohydrin, and the like; chain aliphatic 2,3-epoxypropyloxycompounds such as bis(2,3-epoxypropyl) ether,bis(2,3-epoxypropyloxy)methane, 1,2-bis(2,3-epoxypropyloxy)ethane,1,2-bis(2,3-epoxypropyloxy)propane, 1,3-bis(2,3-epoxypropyloxy)propane,1,3-bis(2,3-epoxypropyloxy)-2-methylpropane,1,4-bis(2,3-epoxypropyloxy)butane,1,4-bis(2,3-epoxypropyloxy)-2-methylbutane,1,3-bis(2,3-epoxypropyloxy)butane, 1,5-bis(2,3-epoxypropyloxy)pentane,1,5-bis(2,3-epoxypropyloxy)-2-methylpentane,1,5-bis(2,3-epoxypropyloxy)-3-thiapentane,1,6-bis(2,3-epoxypropyloxy)hexane,1,6-bis(2,3-epoxypropyloxy)-2-methylhexane,3,8-bis(2,3-epoxypropyloxy)-3,6-dithiaoctane,1,2,3-tris(2,3-epoxypropyloxy)propane,2,2-bis(2,3-epoxypropyloxy)-1,3-bis(2,3-epoxypropyloxymethyl)propane,2,2,-bis(2,3-epoxypropyloxymethyl)-1-(2,3-epoxypropyloxy)butane,1,5-bis(2,3-epoxypropyloxy)-2-(2,3-epoxypropyloxymethyl)-3-thiapentane,1,5-bis(2,3-epoxypropyloxy)-2,4-bis(2,3-epoxypropyloxymethyl)-3-thiapentane,1-(2,3-epoxypropyloxy)-2,2-bis(2,3-epoxypropyloxymethyl)-4-thiahexane,1,5,6-tris(2,3-epoxypropyloxy)-4-(2,3-epoxypropyloxymethyl)-3-thiahexane,1,8-bis(2,3-epoxypropyloxy)-4-(2,3-epoxypropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropyloxy)-4,5-bis(2,3-epoxypropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropyloxy)-4,4-bis(2,3-epoxypropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropyloxy)-2,5-bis(2,3-epoxypropyloxymethyl)-3,6-dithiaoctane,1,8-bis(2,3-epoxypropyloxy)-2,4,5-tris(2,3-epoxypropyloxymethyl)-3,6-dithiaoctane,1,1,1-tris[[2-(2,3-epoxypropyloxy)ethyl]thiomethyl]-2-(2,3-epoxypropyloxy)ethane,1,1,2,2-tetrakis[[2-(2,3-epoxypropyloxy)ethyl]thiomethyl]ethane,1,11-bis(2,3-epoxypropyloxy)-4,8-bis(2,3-epoxypropyloxymethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epoxypropyloxy)-4,7-bis(2,3-epoxypropyloxymethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epoxypropyloxy)-5,7-bis(2,3-epoxypropyloxymethyl)-3,6,9-trithiaundecane,and the like; alicyclic 2,3-epoxypropyloxy compounds such as1,3-bis(2,3-epoxypropyloxy)cyclohexane,1,4-bis(2,3-epoxypropyloxy)cyclohexane,1,3-bis(2,3-epoxypropyloxymethyl)cyclohexane,1,4-bis(2,3-epoxypropyloxymethyl)cyclohexane,2,5-bis(2,3-epoxypropyloxymethyl)-1,4-dithiane,2,5-bis[[2-(2,3-epoxypropyloxy)ethyl]thiomethyl]-1,4-dithiane,2,5-bis(2,3-epoxypropyloxymethyl)-2,5-dimethyl-1,4-dithiane, and thelike; aromatic 2,3-epoxypropyloxy compounds such as1,2-bis(2,3-epoxypropyloxy)benzene, 1,3-bis(2,3-epoxypropyloxy)benzene,1,4-bis(2,3-epoxypropyloxy)benzene,1,2-bis(2,3-epoxypropyloxymethyl)benzene,1,3-bis(2,3-epoxypropyloxymethyl)benzene,1,4-bis(2,3-epoxypropyloxymethyl)benzene,bis[4-(2,3-epoxypropyloxy)phenyl]methane,2,2-bis[4-(2,3-epoxypropyloxy)phenyl]propane,bis[4-(2,3-epoxypropyloxy)phenyl] sulfide,bis[4-(2,3-epoxypropyloxy)phenyl] sulfone,4,4′-bis(2,3-epoxypropyloxy)biphenyl, and the like. However, the epoxidecompounds are not limited to these examples.

Examples of an amine compound which can be added as the resin modifierinclude monofunctional primary amine compounds such as ethylamine,n-propylamine, isopropylamine, n-butylamine, sec-butylamine,tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine,decylamine, laurylamine, myristylamine, 3-pentylamine,2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine,aminomethylbicylcoheptane, cyclopentylamine, cyclohexylamine,2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline,benzylamine, phenethylamine, 2,3- or 4-methylbenzylamine, o-, m- orp-methylaniline, o-, m- or p-ethylaniline, aminomorpholine,naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine,aminopyridine, aminophenol, aminoethanol, 1-aminopropanol,2-aminopropanol, aminobutanol, aminopentanol, aminohexanol,methoxyethylamine, 2-(2-aminoethoxy)ethanol, 3-ethoxypropylamine,3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine,3-isobutoxypropylamine, 2,2-diethoxyethylamine, and the like; primarypolyamine compounds such as ethylenediamine, 1,2- or 1,3-diaminopropane,1,2-, 1,3- or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3- or1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4- or4,4′-diaminobenzophenone, 3,4- or 4,4′-diaminodiphenyl ether,4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′- or4,4′-diaminodiphenyl sulfone, 2,7-diaminofluorene, 1,5-, 1,8- or2,3-diaminonaphthalene, 2,3-, 2,6- or 3,4-diaminopyridine, 2,4- or2,6-diaminotoluene, m- or p-xylylenediamine, isophoronediamine,iaminomethylbicylcoheptane, 1,3- or 1,4-diaminomethylcyclohexane, 2- or4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine,and the like; monofunctional secondary amine compounds such asdiethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine,diisobutylamine, di-n-pentylamine, di-3-penthylamine, dihexylamine,dioctylamine, di(2-ethylhexyl)amine, methylhexylamine, diallylamine,N-methylallylamine, piperidine, pyrrolidine, diphenylamine,N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine,N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N-ethylaniline,dinaphthylamine, 1-methylpiperazine, morpholine, and the like; secondarypolyamine compounds such as N,N′-dimethylethylenediamine,N,N′-dimethyl-1,2-diaminopropane, N,N′-dimethyl-1,3-diaminopropane,N,N′-dimethyl-1,2-diaminobutane, N,N′-dimethyl-1,3-diaminobutane,N,N′-dimethyl-1,4-diaminobutane, N,N′-dimethyl-1,5-diaminopentane,N,N′-dimethyl-1,6-diaminohexane, N,N′-dimethyl-1,7-diaminoheptane,N,N′-diethylethylenediamine, N,N′-diethyl-1,2-diaminopropane,N,N′-diethyl-1,3-diaminopropane, N,N′-diethyl-1,2-diaminobutane,N,N′-diethyl-1,3-diaminobutane, N,N′-diethyl-1,4-diaminobutane,N,N′-diethyl-1,5-diaminopentane, N,N′-diethyl-1,6-diaminohexane,N,N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine,2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine,1,1-di-(4-piperidyl)methane, 1,2-di-(4-piperidyl)ethane,1,3-di-(4-piperidyl)propane, 1,4-di-(4-pieridyl)butane,tetramethylguanidine, and the like. However, the amine compounds are notlimited to these examples. The amine compounds may be used singly or ina mixture of at least two compounds. Of these compound examples,benzylamine and piperazines are more preferred compounds.

A thiol compound which can be added as the resin modifier may contain atleast one sulfur atom other than a mercapto group. Examples of amonofunctional thiol compound include aliphatic mercaptan compounds suchas methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan,octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, hexadecylmercaptan, octadecyl mercaptan, cyclohexyl mercaptan, benzyl mercaptan,ethylphenyl mercaptan, 2-mercaptomethyl-1,3-dithiolane,2-mercaptomethyl-1,4-dithiane, and the like; aromatic mercaptancompounds such as thiophenol, mercaptotoluene, and the like. Examples ofa di- or higher-functional polythiol compounds include aliphaticpolythiol compounds such as 1,1-methanedithiol, 1,2-ethanedithiol,1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol,2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propantrithiol,1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol,2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol,2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane,thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercapto-1-propanol(2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoproprionate),diethylene glycol bis(2-mercaptoacetate), diethylene glycolbis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether,2,3-dimercaptopropyl methyl ether,2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether,ethylene glycol bis(2-mercaptoacetate), ethylene glycolbis(3-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate),trimethylolpropane bis(3-mercaptopropionate), pentaerythritoltetrakis(2-mercaptoacetate), pentaerythritoltetrakis(3-mercaptopropionate), tetrakis(mercaptomethyl)methane, and thelike; aromatic polythiol compounds such as 1,2-dimercaptobenzene,1,3-dimercaptobenzene, 1,4-dimercaptobenzene,1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene,1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene,1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene,1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene,1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene,1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene,1,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol,3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol,1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol,2,4-di(p-mercaptophenyl)pentane, and the like; polythiols each having aheterocycle, such as 2-methylamino-4,6-dithiol-sym-triazine, and thelike; aromatic polytiol compounds each having a sulfur atom other than amercapto group, such as 1,2-bis(mercaptoethylthio)benzene,1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene,1,2,3-tris(mercaptomethylthio)benzene,1,2,4-tris(mercaptomethylthio)benzene,1,3,5-tris(mercaptomethylthio)benzene,1,2,3-tris(mercaptoethylthio)benzene,1,2,4-tris(mercaptoethylthio)benzene,1,3,5-tris(mercaptoethylthio)benzene, and the like, nuclear alkylatedproducts thereof; aliphatic polythiol compounds each having a sulfurgroup other than a mercapto group, such as bis(mercaptomethyl) sulfide,bis(mercaptoethyl) sulfide, bis(mercaptopropyl) sulfide,bis(mercaptomethylthio) methane, bis(2-mercaptoethylthio)methane,bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane,1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropyl)ethane,1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane,1,3-bis(3-mercaptopropylthio)propane,1,2,3-tris(mercaptomethylthio)propane,1,2,3-tris(2-mercaptoethylthio)propane,1,2,3-tris(3-mercaptopropylthio)propane,1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane,4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,5,7-dimercaptomethyl-1.,l1-mercapto-3,6,9-trithiaundecane,tetrakis(mercaptomethylthiomethyl)methane,tetrakis(2-mercaptoethylthiomethyl)methane,tetrakis(3-mercaptopropylthiomethyl)methane,1,1,2,2-tetrakis(mercaptomethylthio)ethane,1,1,3,3-tetrakis(mercaptomethylthio)propane, bis(2,3-dimercaptopropyl)sulfide, bis(1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane,2,5-dimercaptomethyl-1,4-dithiane,2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane,4,6-bis(mercaptomethylthio)-1,3-dithiane, bis(mercaptomethyl) disulfide,bis(mercaptoethyl) disulfide, bis(mercaptopropyl) disulfide, and thelike, thioglycolic acid and mercaptopropionic acid esters of thesepolytiol compounds, hydroxymethyl sulfide bis(2-mercaptoacetate),hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfidebis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate),hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfidebis(3-mercaptopropionate), hydroxymethyl disulfidebis(2-mercaptoacetate), hydroxymethyl disulfidebis(3-mercaptoproprionate), hydroxyethyl disulfidebis(2-mercaptoacetate), hydroxyethyl disulfidebis(3-mercaptopropionate), hydroxypropyl disulfidebis(2-mercaptoacetate), hydroxypropyl disulfidebis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate),2-mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diolbis(2-mercaptoacetate), 1,4-dithiane-2,5-diol bis(3-mercaptopropionate),thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acidbis(2-mercaptoethyl ester), 4,4-thiodibutyric acid bis(2-mercaptoethylester), dithiodiglycolic acid bis(2-mercaptoethyl ester),dithiodipropionic acid bis(2-mercaptoethyl ester), 4,4-dithiodibutyricacid bis(2-mercaptoethyl ester), thiodiglycolic acidbis(2,3-dimercaptopropyl ester), thiodipropionic acidbis(2,3-dimercaptopropyl ester), dithioglycolic acidbis(2,3-dimercaptopropyl ester), dithiodipropionic acidbis(2,3-dimercaptopropyl ester), and the like; heterocyclic compoundseach having a sulfur atom other than a mercapto group, such as3,4-thiophenedithiol, 2,5-dimercapto-1,3,4-thiadiazole, Bismuthiol, andthe like.

Examples of a mercapto compound having a hydroxyl group include2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerindi(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane,2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol,1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol,1,2-dimercapto-1,3-butanediol, pentaerythritoltris(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate),pentaerythritol bis(3-mercaptopropionate), pentaerythritoltris(thioglycolate), dipentaerythritol pentakis(3-mercaptopropionate),hydroxymethyl-tris(mercaptoethylthiomethyl)methane,1-hydroxyethylthio-3-mercaptoethylthiobenzene, and the like. However,the thiol compounds are not limited to these examples. Also, halogenatedproducts of these polythiol compounds, such as chlorinated andbrominated products, may be used. These compounds may be used singly orin a mixture of at least two compounds. Of these thiol compounds,polysulfide-type polythiol compounds are preferred from the viewpoint ofthe refractive index of the resultant resin. Polythiol compoundscomposed of only carbon, hydrogen and sulfur atoms are more preferred.In consideration of the heat resistance of the resulting resin, thecompounds are more preferably di- or higher-functional rather thanmonofunctional, and most preferably tetra- or higher-functional.Preferred examples of these compounds include bis(mercaptomethyl)sulfide, 1,1,2,2-tetrakis(mercaptomethylthio)ethane,1,1,3,3-tetrakis(mercaptomethylthio)propane,4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, and the like.

Examples of hydroxy compounds including phenol compounds used as theresin modifier in the present invention are mono- or higher-functionalmono or polyol compounds including compounds having phenolic hydroxylgroups. The hydroxy compounds also include compounds each having asulfur atom in its molecule. Examples of monofunctional compoundsinclude aliphatic monofunctional alcohol compounds such as methanol,ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol,pentanol, isoamyl alcohol, hexanol, heptanol, octanol, nonyl alcohol,decanol, dodecyl alcohol, cetyl alcohol, isotridecyl alcohol, stearylalcohol, 2-ethyl-1-hexanol, ally alcohol, methoxyethanol, ethoxyethanol,phenoxyethanol, cyclopropanol, cyclobutanol, cyclopentanol,cyclohexanol, cyclooctanol, benzyl alcohol, phenylethyl alcohol,methylcyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, methyllactate, ethyl lactate, butyl lactate, and the like; aromaticmonofuctional phenol compounds such as phenol, cresol, ethylphenol,methoxyphenol, ethoxyphenol, methoxyethylphenol, cumylphenol,phenoxyphenol, tert-butylphenol, naphthol, and the like.

Examples of di- or higher-functional polyol compounds include polyolssuch as ethylene glycol, diethylene glycol, propylene glycol,dipropylene glycol, butylene glycol, neopentyl glycol, glycerin,trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglycoside, pentaerythritol, dipentaerythritol, tripentaerythritol,sorbitol, erythritol, threitol, mannitol, ribitol, arabinitol, xylitiol,allitol, dorsitol, glycol, inositol, hexane triol, triglycerol,triethylene glycol, polyethylene glycol, tris(2-hydroxyethyl)isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol,cycloheptanediol, cyclooctanediol, cyclohexanedimethaol,hydroxypropylcyclohexanol, bicyclo[4,3,0]-nonanediol, dicylcohexanediol,tricyclo[5,3,1,1]dodecanediol, bicyclo[4,3,0]-nonanedimethanol,dicylcohexanediol, tricyclo[5,3,1,1]dodecanediethanol,spiro[3,4]octanediol, butylcyclohexanediol, 1,1-bicyclohexylidenediol,cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene,trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene,benzenetriol, biphenyltetraol, trihydroxyphenanthrene, bisphenol A,bisphenol F, xylylene glycol, bis(2-hydroxyethoxy)benzene, bisphenolA-bis(2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenolA-bis(2-hydroxyethyl ether), dibromoneopentyl glycol, and the like;condensation reaction products of these polyols with organic polybasicacids such as oxalic acid, glutamic acid, adipic acid, acetic acid,propionic acid, phthalic acid, isophthalic acid, salicylic acid,pyromellitic acid, 3-bromopropionic acid, 2-bromoglycolic acid,dicarboxycyclohexane, butanetetracarboxylic acid, bromophthalic acid,and the like; addition reaction products of the polyols with alkyleneoxides such as ethylene oxide, propylene oxide, and the like. However,the polyol compounds are not limited to these examples. Furthermore,halogenated products of these polyols, such as chlorinated products,brominated products, and the like, may be used.

Examples of mono or polyol compounds each having a sulfur atom includebis[4-(hydroxyethoxy)phenyl] sulfide, bis[4-(2-hydroxypropoxy)phenyl]sulfide, bis[4-(2,3-dihydroxypropoxy)phenyl] sulfide,bis[4-(4-hydroxycyclohexyloxy)phenyl] sulfide, andbis[2-methyl-4-(hydroxyethoxy)-6-butylphenyl] sulfide, and compoundshaving an average of 3 or less molecules of ethylene oxide and/orpropylene oxide per hydroxyl group, which are added to these mono orpolyol compounds, bis(2-hydroxyethyl) sulfide,1,2-bis(2-hydroxyethylmercapto)ethane, bis(2-hydroxyethyl) disulfide,1,4-dithiane-2,5-diol, bis(2,3-dihydroxypropyl) sulfide,tetrakis(4-hydroxy-2-thiabutyl)methane, bis(4-hydroxyphenyl) sulfone(bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S,4,4-thiobis(6-tert-butyl-3-methylphenol),1,3-bis(2-hydroxyethylthioethyl)cyclohexane, and the like. However, thepolyol compounds are not limited to these examples. Furthermore,halogenated products of these compounds, such as chlorinated productsand brominated products, may be used.

Examples of an iso(thio)cyanate compound used as the resin modifier inthe present invention include monofunctional isocyanate compounds suchas methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropylisocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butylisocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate,octyl isocyanate, decyl isocyanate, lauryl isocyanate, myristylisocyanate, octadecyl isocyanate, 3-pentyl isocyanate, 2-ethylhexylisocyanate, 2,3-dimethylcyclohexyl isocyanate, 2-methoxyphenylisocyanate, 4-methoxyphenyl isocyanate, α-methylbenzyl isocyanate,phenylethyl isocyanate, phenyl isocyanate, o-, m- or p-tolyl isocyanate,cyclohexyl isocyanate, benzyl isocyanate,isocyanatomethylbicycloheptane, and the like; aliphatic polyisocyanatecompounds such as hexamethylene diisocyanate, 2,2-dimethylpentanediisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate,1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylenediisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane,bis(isocyanatoethyl) carbonate, bis(isocyanatoethyl) ether, lisinediisocyanatomethyl ester, lisine triisocyanate, xylylene diisocyanate,bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, α, α, α′,α′-tetramethylxylylene diisocyanate, bis(isocyanatobutyl)benzene,bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether,bis(isocyanatoethyl) phthalate, mesitylene triisocyanate,2,6-di(isocyanatomethyl)furan, and the like; alicyclic polyisocyanatecompounds such as isophorone diisocyanate,bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate,cyclohexane diisocyanate, methylcyclohexane diisocyanate,dicyclohexyldimethylmethane diisocyanate,2,2-dimethyldicyclohexylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2,2,1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2,2,1]-heptane, 3,8-bis(isocyanatomethyl) tricyclodecane,3,9-bis(isocyanatomethyl) tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, 4,9-bis(isocyanatomethyl) tricyclodecane, and the like;aromatic polyisocyanate compounds such as phenylene diisocyanate,tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylenediisocyanate, dimethylphenylene diisocyanate, diethylphenylenediisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidinediisocyanate, 4,4-diphenylmethane diisocyanate,3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate,bis(isocyanatophenyl)ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate,phenylisocyanatoethyl isocyanate, hexahydrobenzene diisocyanate,hexahydrodiphenylmethane-4,4-diisocyanate, and the like;sulfur-containing aliphatic isocyanate compounds such asbis(isocyanatomethyl) sulfide, bis(isocyanatoethyl) sulfide,bis(isocyanatopropyl) sulfide, bis(isocyanatohexyl) sulfide,bis(isocyanatomethyl) sulfone, bis(isocyanatomethyl) disulfide,bis(isocyanatoethyl) disulfide, bis(isocyanatopropyl) disulfide,bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane,bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane,1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, and the like;aromatic sulfide-type isocyanate compounds such asdiphenylsulfido-2,4-diisocyanate, diphenylsulfido-4,4-diisocyanate,3,3-dimethoxy-4,4-diisocyanatodibenzyl thioether,bis(4-isocyanatomethylbenzene) sulfide, 4,4-methoxybenzene thioethyleneglycol-3,3-diisocyanate, and the like; aromatic disulfide-typeisocyanate compounds such as diphenyl disufido-4,4-diisocyanate,2,2-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfido-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfido-6,6-diisocyanate, 4,4-dimethyldiphenyldisulfido-5,5-diisocyanate, 3,3-dimethoxydiphenyldisulfido-4,4-diisocyanate, 4,4-dimethoxydiphenyldisulfido-3,3-diisocyanate, and the like; sulfur-containing heterocycliccompounds such as 2,5-diisocyanatothiophene,2,5-bis(isocyanatomethyl)thiophene, and the like.

Other examples include 2,5-diisocyanatotetrahydrothiophene,2,5-bis(isocyanatomethyl)tetrahydrothiophene,3,4-bis(isocyanatomethyl)tetrahydrothiophene,2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane,4,5-diisocyanato-1,3-dithiolane,4,5-bis(isocyanatomethyl)-1,3-dithiolane,4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane, and the like.However, the isocyanate compounds are not limited to these examples.Also, halogenated products such as chlorinated products and brominatedproducts, alkylated products, alkoxylated products, nitro-substitutedproducts, prepolymer-type modified products with polyhydric alcohols,carbodiimide-modified products, urea-modified products, burette-modifiedproducts, dimerization or trimerization reaction products of thesecompounds may be used.

Examples of isothiocyanate compounds include monofunctionalisothiocyanate compounds such as methyl isothiocyanate, ethylisothiocyanate, n-propyl isothiocyanate, isopropyl isothiocyanate,n-butyl isothiocyanate, sec-butyl isothiocyanate, tert-butylisothiocyanate, pentyl isothiocyanate, hexyl isothiocyanate, heptylisothiocyanate, octyl isothiocyanate, decyl isothiocyanate, laurylisothiocyanate, myristyl isothiocyanate, octadecyl isothiocyanate,3-pentyl isothiocyanate, 2-ethylhexyl isothiocyanate,2,3-dimethylcyclohexyl isothiocyanate, 2-methoxyphenyl isothiocyanate,4-methoxyphenyl isothiocyanate, α-methylbenzyl isothiocyanate,phenylethyl isothiocyanate, phenyl isothiocyanate, o-, m- or p-tolylisothiocyanate, cyclohexyl isothiocyanate, benzyl isothiocyanate,isothiocyanatomethylbicycloheptane, and the like; aliphaticpolyisothiocyanate compounds such as 1,6-diisothiocyanatohexane,p-phenyleneisopropylidene diisothiocyanate, and the like; alicyclicpolyisothiocyanate compounds such as cyclohexane diisothiocyanate,diisothiocyanatomethylbicycloheptane, and the like; aromaticisothiocyanate compounds such as 1,2-diisothiocyanatobenzene,1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene,2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene,4,4-diisothiocyanato-1,1-biphenyl, 1,1-methylenebis(4-isothiocyanatobenzene), 1,1-methylenebis(4-isothiocyanato-2-methylbenzene), 1,1-methylenebis(4-isothiocyanato-3-methylbenzene), 1,1-(1,2-ethanediyl) bis(isothiocyanatobenzene), 4,4-diisothiocyanatobenzophenone,4,4-diisothiocyanato-3,3-dimethylbenzophenone, diphenylether-4,4-diisothiocyanate, diphenylamine-4,4-diisothiocyanate, and thelike; carbonyl isothiocyanate compounds such as 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyl diisothiocyanate,(2,2-pyridine)-4,4-dicarbonyl diisothiocyanate, and the like. However,the isothiocyanate compounds are not limited to these examples.

Examples of an isothiocyanate compound having one or more sulfur atomsother than an isothiocyanato group include sulfur-containing aliphaticisothiocyanate compounds such as thiobis(3-isothiocyanatopropane),thiobis(2-isothiocyanatoethane), dithiobis(2-isothiocyanatoethane), andthe like; sulfur-containing aromatic isothiocyanate compounds such as1-isothiocyanato-4-[(2-isothiocyanato)sulfonyl]benzene,thiobis(4-isothiocyanatobenzene), sulfonyl bis(4-isothiocyanatobenzene),dithiobis(4-isothiocyanatobenzene), and the like; sulfur-containingheterocyclic compounds such as 2,5-diisothiocyanatothiophene,2,5-diisothiocyanato-1,4-dithiane, and the like. However, thesulfur-containing isothiocyanate compounds are not limited to theseexamples. Also, halogenated products such as chlorinated products andbrominated products, alkylated products, alkoxylated products,nitro-substituted products, prepolymer-type modified products withpolyhydric alcohols, carbodiimide-modified products, urea-modifiedproducts, burette-modified products, dimerization or trimerizationreaction products of these compounds may be used.

Examples of an isothiocyanate compound having an isocyanato groupinclude aliphatic and alicyclic compounds such as1-isocyanato-6-isothiocyanatohexane,1-isocyanato-4-isothiocyanatocyclohexane, and the like; aromaticcompounds such as 1-isocyanato-4-isothiocyanatobenzene,4-methyl-3-isocyanato-1-isothiocyanatobenzene, and the like;heterocyclic compounds such as2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and the like; andcompounds each having a sulfur atom other than an isothiocyanato group,such as 4-isocyanato-4′-isothiocyanatodiphenyl sulfide,2-isocyanato-2′-isothiocyanatodiethyl disulfide, and the like. However,the isothiocyanate compounds each having an isocyanato groups are notlimited to these examples. Also, halogenated products such aschlorinated products and brominated products, alkylated products,alkoxylated products, nitro-substituted products, prepolymer-typemodified products with polyhydric alcohols, carbodiimide-modifiedproducts, urea-modified products, burette-modified products,dimerization or trimerization reaction products of these compounds maybe used.

Preferred examples of a mercapto organic acid compound used as the resinmodifier in the present invention include thioglycolic acid,3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalicacid, thiosalicylic acid, and the like. However, the mercapto organicacids are not limited to these examples. Also, the mercapto organic acidcompounds may be used singly or in a mixture of at least two compounds.

Preferred examples of organic acids and anhydrides thereof includemonofunctional organic acids such as hydrocarbon organic acids, such asformic acid, acetic acid, propionic acid, butyric acid, benzoic acid,p-toluenesulfonic acid, methanesulfonic acid, and the like, andhalogen-, nitro- and cyano-substituted products thereof; acid anhydridessuch as trifluoroacetic anhydride, chloroacetic anhydride,dichloroacetic anhydride, trichloroacetic anhydride, phthalic anhydride,hexahydrophthalic anhydride, methylhexahydrophthalic anhydride,methyltetrahydrophthalic anhydride, methylnorbornene acid anhydride,methylnorbornane acid anhydride, maleic anhydride, trimelliticanhydride, pyromellitic anhydride, and the like; difunctional organicacids such as phthalic acid, succinic acid, and the like;sulfur-containing organic acids such as thiodiglycolic acid,thiodipropionic acid, dithiodipropionic acid, and the like. However, theorganic acids are not limited to these examples.

Preferred examples of olefins include (meth)acrylate compounds such asbenzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethylmethacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidylacrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethylmethacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethyleneglycol dimethacrylate, diethylene glycol diacrylate, diethylene glycoldimethacrylate, triethylene glycol diacrylate, triethylene glycoldimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, polyethylene glycol diacrylate, polyethyelne glycoldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycolbisglycidyl methacrylate, bisphenol A diacrylate, bisphenol Adimethacrylate, 2,2-bis(4-acryloxyethoxyphenyl)propane,2,2-bis(4-methacryloxyethoxyphenyl)propane,2,2-bis(4-acryloxydiethoxyphenyl)propane,2,2-bis(4-methacryloxydiethoxyphenyl)propane, bisphenol F diacrylate,bisphenol F dimethacrylate, 1,1-bis(4-acryloxyethoxyphenyl)methane,1,1-bis(4-methacryloxyethoxyphenyl)methane,1,1-bis(4-acryloxydiethoxyphenyl)methane,1,1-bis(4-methacryloxydiethoxyphenyl)methane, dimethyloltricyclodecanediacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, glycerol diacrylate, glycerol dimethacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,pentaerythritol tetramethacrylate, methyl thioacrylate, methylthiomethacrylate, phenyl thioacrylate, benzyl thiomethacrylate,xylyleneditiol diacrylate, xylyleneditiol dimethacrylate, mercaptoethylsulfide diacrylate, mercaptoethyl sulfide dimethacrylate, and the like;ally compounds such as ally diglycidyl ether, dially phthalate, diallyterephthalate, dially isophthalate, dially carbonate, diethylene glycolbisally carbonate, and the like; vinyl compounds such as styrene,chlorostyrene, methylstyrene, bromostyrene, dibromostyrene,divinylbenzene, 3,9-divinyl spirobi(m-dioxane), divinyl sulfide, divinyldisulfide, and the like; diisopropenylbenzene; and the like. However,the olefins are not limited to these examples.

Furthermore, the above-described several types of resin modifiers may beused singly or in a mixture of at least two types. Although the amountof the resin modifiers added depends upon the structure of a compoundconstituting the polymerizable composition and is not limited, theamount is usually in the range of 0.001 wt % to 50 wt % based on theamount of the polymerizable composition. The adding amount is preferably0.005 wt % to 25 wt %, and more preferably 0.01 wt % to 15 wt %.

The polymerizable composition containing the sulfur-containing cycliccompound having the structure represented by formula (1) of the presentinvention can be cured by a known method for polymerizing asulfur-containing cyclic compound. The type and amount of the curingcatalyst used for obtaining a cured resin, and the type and ratio of themonomer used depend upon the structure of a compound constituting thepolymerizable composition and are not limited. However, as the type ofthe curing catalyst, amines other than the resin modifier used in thepresent invention, phosphines, organic acids and salts, esters,anhydrides thereof, inorganic acids, quaternary ammonium salts,quaternary phosphonium salts, tertiary sulfonium salts, secondaryiodonium salts, Lewis acids, radical polymerization catalysts, cationicpolymerization catalysts, and the like are conventionally used.

Examples of the curing catalyst include aliphatic and aromatic tertiaryamines such as triethylamine, tri-n-butylamine, tri-n-hexylamine,N,N-diisopropylethylamine, triethylenediamine, triphenylamine,N,N-dimethylethanolamine, N,N-diethylethanolamine,N,N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine,N,N-dimethylbenzylamine, N,N-diethylbenzylamine, tribenzylamine,N-methyldibenzylamine, N,N-dimethylcyclohexylamine,N,N-diethylcyclohexylamine, N,N-dimethylbutylamine,N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine,pyridine, quinoline, N,N-dimethylaniline, N,N-diethylaniline, α-, β- orγ-picoline, 2,2′-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide,tetramethylethylenediamine, hexamethylenetetramine,1,8-diazabicyclo(5,4,0)-7-undecene,2,4,6-tris(N,N-dimethylaminomethyl)phenol, and the like; phosphines suchas trimethylphosphine, triethylphosphine, tri-n-propylphosphine,triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine,tribenzylphosphine, 1,2-bis(diphenylphosphino)ethane,1,2-bis(dimethylphosphino)ethane, and the like; trihalogenoacetic acidsand esters, anhydrides and salts thereof, such as trifluoroacetic acid,trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate,sodium trifluoroacetate, and the like; p-toluenesulfonic acid;methanesulfonic acid; trihalogenomethanesulfonic acids and esters,anhydrides and salts thereof, such as trifluoromethanesulfonic acid,trifluoromethanesulfonic anhydride, ethyl trifluoromethanesulfonate,sodium trifluoromethanesulfonate, and the like; inorganic acids such ashydrochloric acid, sulfuric acid, nitric acid, and the like; quaternaryammonium salts such as tetramethylammonium chloride, tetrabutylammoniumchloride, tetrabutylammonium bromide, and the like; quaternaryphosphonium salts such as tetramethylphosphonium chloride,tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and thelike; tertiary sulfonium salts, such as trimethylsulfonium bromide,tributylsulfonium bromide, and the like; secondary iodonium salts suchas diphenyliodonium bromide, and the like; Lewis acids such asdimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate,dibutyltin diacetate, tetrachlorotin, dibutyltin oxide,diacetoxytetrabutyldistannoxane, zinc chloride, acetylacetone zinc,aluminum chloride, aluminum fluoride, triphenyl aluminum, acetylacetonealuminum, isopropoxide aluminum, tetrachlorotitanium and complexesthereof, tetraiodotitanium, titanium alkoxides such as dichlorotitaniumdiisopropoxide, titanium isopropoxide, and the like, calcium acetate,boron trihalide compounds such as boron trifluoride, boron trifluoridediethyl ether complex, boron trifluoride piperidine complex, borontrifluoride ethyleneamine complex, boron trifluoride acetic acidcomplex, boron trifluoride phosphoric acid complex, boron trifluoridet-butyl methyl ether complex, boron trifluoride dibutyl ether complex,boron trifluoride THF complex, boron trifluoride methyl sulfide complex,boron trifluoride phenol complex, and the like, boron trichloridecomplexes, and the like; radial polymerization catalysts such as2,2′-azobis(2-cyclopropylpropionitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis(2,4-dimethylvaleronitrile), t-butylperoxy-2-ethylhexanoate,n-butyl-4,4′-bis(t-butylperoxy)valerate, t-butylperoxybenzoate, and thelike; cationic polymerization catalysts such as diphenyliodoniumhexafluorophosphate, diphenyliodonium hexafluoroarsenate,diphenyliodonium hexafluoroantimony, triphenylsulfoniumtetrafluoroborate, triphenylsulfonium hexafluorophosphate,triphenylsulfonium hexafluoroarsenate, (tolylcumyl)iodoniumtetrakis(pentafluorophenyl)borate, and the like. However, the curingcatalysts are not limited to these examples.

The above-described curing catalysts may be used singly or in a mixtureof at least two compounds. A mixture of at least two types of curingcatalysts having different reactivities is preferably used for improvingthe monomer handleability, and the optical physical properties, hue,transparency, and optical strain (stria) of the resultant resin in somecases.

Of the above compounds, preferred examples include organotin compoundssuch as dimethyltin dichloride, dibutyltin dichloride, dibutyltindilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide,diacetoxytetrabutylstannoxane, and the like; trihalogenoacetic acids andesters, anhydrides and salts thereof, such as trifluoroacetic acid,trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate,sodium trifluoroacetate, and the like; p-toluenesulfonic acid;methanesulfonic acid; trihalogenomethanesulfonic acids and esters,anhydrides and salts thereof, such as trifluoromethanesulfonic acid,trifluoromethanesulfonic anhydride, ethyl trifluoromethanesulfonate,sodium trifluoromethanesulfonate, and the like; Lewis acids such asboron trihalides and complexes thereof, such as boron trifluoride; borontrifluoride complexes such as boron trifluoride diethyl ether complex,boron trifluoride piperidine complex, boron trifluoride ethylaminecomplex, boron trifluoride acetic acid complex, boron trifluoridephosphoric acid complex, boron trifluoride t-butyl methyl ether complex,boron trifluoride dibutyl ether complex, boron trifluoride THF complex,boron trifluoride methyl sulfide complex, boron trifluoride phenolcomplex, and the like, boron trichloride and complexes thereof, and thelike; cationic polymerization catalysts such as diphenyliodoniumhexafluorophosphate, diphenyliodonium hexafluoroarsenate,diphenyliodonium hexafluoroantimony, triphenylsulfoniumtetrafluoroborate, triphenylsulfonium hexafluorophosphate,triphenylsulfonium hexafluoroarsenate (tolylcumyl)iodoniumtetrakis(pentafluorophenyl)borate, and the like. Of these compounds,dimethyltin dichloride, trifluoromethanesulfonic acid and anhydrides,esters, and salts thereof, and boron trifluoride complexes are morepreferred.

The amount of the curing catalyst added is in the range of 0.001 wt % to10 wt %, preferably 0.01 wt % to 5 wt %, and more preferably 0.005 wt %to 1 wt %, based on the total weight of the polymerizable composition.With the amount of curing catalyst added in this range, a sufficientlycured resin can be produced, and a pot life can be maintained. Also, theobtained resin has good transparency and optical physical properties insome cases. The curing catalyst may be added directly to any of theabove-described compounds of the present invention, or may be dissolvedor dispersed in another compound and then added. In some cases, thecuring catalyst is preferably dissolved or dispersed in another compoundand then added, for obtaining good results. Furthermore, the curingcatalyst is preferably added in a nitrogen atmosphere or a dry gasatmosphere for obtaining good results in some cases. In order to improvethe performance of the resultant resin, the amount of the unreactivegroups remaining in the resin is preferably 0.5 wt % or less, and morepreferably 0.3 wt % or less, based on the total weight of the resin.

In curing and molding the polymerizable composition containing thesulfur-containing cyclic compound having the structure represented byformula (1) of the present invention, a known molding method may be usedaccording to purposes, and various additives other than theabove-described additives, such as a stabilizer, a resin modifier, achain extender, a crosslinking agent, a HALS-type photostabilizer or thelike, a benzotriazole ultraviolet absorber or the like, a hinderedphenol antioxidant or the like, a coloring inhibitor, an anthraquinonedisperse dye or the like, a filler, a silicone-type external moldreleasing agent or acidic phosphate or quaternary ammonium salt internalmold releasing agent, an adhesion improving agent, and the like may beused. Although the amount of each of the additives which can be addeddepends upon the type, structure and effect of each additive and is notlimited, the adding amount is usually in the range of 0.001 wt % to 10wt %, and preferably 0.01 to 5 wt %, based on the total weight of thepolymerizable composition. The amount of the dye added is preferably inthe range of 1 ppb to 100 ppm, not in the above-described range. Withinthese ranges, a sufficiently cured resin can be produced, and theobtained resin has good transparency and optical physical properties insome cases.

A typical polymerization method for producing a resin (for example, aplastic lens) by curing the composition of the present invention is acasting polymerization. Namely, the polymerizable composition of thepresent invention is injected into a mold which is maintained by agasket, a tape, or the like. Although the injection operation may beperformed in a normal atmosphere unless there is a problem, it ispreferably performed in a nitrogen atmosphere or dry gas atmosphere forproducing good results in some cases. The inside of the mold may bepreviously replaced with a nitrogen gas or dry gas. The polymerizablecomposition may be mixed with the curing catalyst and resin modifier,and subjected to an operation such as a reduced-pressure treatment under10 kPa or less, such as degassing, filtration, or the like according todemand. Next, the composition can be cured by heating in a heatingapparatus such as an oven, water, or the like, and then taken out.

The polymerization method, polymerization conditions, and the like forproducing the resin by curing the composition of the present inventiondepend upon the type and amount of the curing catalyst used, and thetype and ratio of the monomer used, and are not limited.

The heating polymerization conditions for the polymerizable compositioninjected into the mold according to the present invention depend uponthe composition and structure of the polymerizable compositioncontaining a compound having the structure represented by formula (1) ofthe present invention, and are not limited. Also, the conditions greatlydepend upon the type of the resin modifier used, the type of the curingcatalyst used, the shape of the mold, etc., and are not limited.However, the polymerization temperature is about −50° C. to 200° C.,preferably −20° C. to 150° C., and more preferably in the temperaturerange of 0° C. to 130° C. The polymerization time is 0.01 to 100 hours,preferably 0.05 to 50 hours, and more preferably 0.1 to 25 hours. Insome cases, the polymerization conditions can be programmed with a lowtemperature, a temperature rise, a temperature drop, and the like.

The polymerization time of the composition of the present invention canbe reduced by irradiation with an energy beam such as an electron beam,an ultraviolet ray, or the like. In this case, the curing catalyst suchas the radical polymerization catalyst, the cationic polymerizationcatalyst, or the like may be added. Also, the cured resin may besubjected to a treatment such as annealing or the like. Although theannealing condition depends upon the structure of the compoundconstituting the polymerizable composition to be cured, and thestructure of the resultant resin and is not limited, annealing isusually performed at 30° C. to 200° C., preferably 50° C. to 150° C.,and more preferably 70° C. to 130° C.

Furthermore, the resin of the present invention can be molded intovarious shapes by using various molds for casting polymerization, sothat the resin can be used for various applications of a resin requiredto have a high refractive index and transparency, such as eyeglasses, acamera lens, a light emitting diode (LED), and the like. Particularly,the resin is preferably used as an optical material for eyeglasses and acamera lens, and the like.

Furthermore, a lens using the optical material of the present inventioncan be subjected to a physical or chemical treatment such as surfacepolishing, an antistatic treatment, a hard coating treatment, anon-reflecting coating treatment, a dyeing treatment, or the like, forpreventing reflection, imparting high hardness, a defogging property orfashion property, or improving abrasion resistance or chemicalresistance according to demand.

Although the present invention will be described in detail below withreference to examples, the present invention is not limited to theseexamples. The thermal stability of the obtained polymerizablecomposition was. tested by measuring a change in purity of a maincomponent in a heat retention test at 40° C. in a nitrogen atmosphere.One month after, when the purity was decreased by 10% or more, thestability was evaluated as x(not good), and when the purity wasdecreased by 10% or less, the stability was evaluated as ◯ (good). Ofthe performance tests of the resultant cured resin, the optical physicalproperties, specific gravity, optical strain, and impact resistance wereevaluated by the following test methods.

-   -   Refractive index (ne) and Abbe's number (νe); measured with a        Pulfrich's refractometer at 20° C.    -   Specific gravity: Measured by an Archimedes method at 20° C.    -   Optical strain: Visually observed under a high-pressure mercury        lamp.    -   Impact resistance: A iron ball of 16 g was dropped on a lens        (−3D) having a central thickness of about 1.0 mm from a height        of 127 cm, and a damage state of the lens was observed. A        damaged lens was evaluated as × (not good), and an undamaged        lens was evaluated as ◯ (good)

EXAMPLE 1

190 g of thiourea, 253 g of 35% hydrochloric acid, and 250 g of waterwere charged in a reactor provided with a stirrer and thermometer, andthen 156 g of 3-thietanol was added dropwisely to the resultant mixtureunder stirring. The mixture was further stirred at 30° C. for 24 hoursfor aging. Then, 177 g of 24% ammonia water was added dropwisely to themixture maintained at 30° C., and then stirred at 30° C. for 15 hoursfor aging. After still standing, 134 g of a lower layer was removed asan organic layer. The thus-removed lower layer was simply distilledunder reduced pressure to recover a distillate of 40° C. under 106 Pa.As a result, 69 g of distillate was obtained, and the distillate was3-mercaptothietane (referred to as “compound A” hereinafter).

The identification data of compound A is shown below. TABLE 1 ElementalAnalysis C H S Theoretical 33.9% 5.7% 60.4% value Analytical 34.2% 5.1%60.7% value MS spectrum (EI M⁺ = 106 method) IR spectrum 642 cm⁻¹;sulfide 2539 cm⁻¹; mercaptan ¹H-NMR spectrum a; 2.1 ppm(1H) (CDCL₃) b;3.4 ppm(4H) c; 4.3 ppm(1H) ¹³C-NMR spectrum 1; 37.6 ppm (CDCL₃) 2; 39.3ppm

EXAMPLE 2

163 g of 3-chlorothietane (referred to as “compound B” hereinafter) and200 g of toluene were charged in a reactor provided with a stirrer andthermometer, and then a sodium sulfide aqueous solution obtained byreacting 60 g of 70% sodium hydrosulfide, 60 g of water and 62 g of 49%caustic soda was added dropwisely to the resultant mixture understirring at 5° C. After aging for 2 hours, the resultant toluene layerwas washed with acetic acid and a salt aqueous solution, dehydrated withmagnesium sulfate, and then concentrated to obtain 135 g ofconcentration residue. The thus-obtained residue was purified by silicagel chromatography using hexane and chloroform as developing solvents.As a result of analysis, 84 g of bis(3-thietanyl) sulfide (referred toas “compound C” hereinafter) was obtained. The stability of thethus-obtain compound C was evaluated as ◯ (good).

The identification data of compound C is shown below. TABLE 2 ElementalAnalysis C H S Theoretical 40.5% 5.6% 53.9% value Analytical 41.6% 5.2%53.2% value MS spectrum (EI M⁺ = 178 method) IR spectrum 653 cm⁻¹;sulfide ¹H-NMR spectrum a; 3.2 ppm(4H) (CDCL₃) b; 3.5 ppm(4H) c; 4.2ppm(2H) ¹³C-NMR spectrum 1; 34.5 ppm (CDCL₃) 2; 43.5 ppm

EXAMPLE 3

159 g of compound A and 20 g of toluene were charged in a reactorprovided with a stirrer and thermometer, and then 890 g of 12.7% sodiumhypochlorite aqueous solution was added dropwisely to the resultantmixture under stirring at 10° C. After aging at 10° C. for 2 hours, theresultant toluene layer was washed twice with a salt aqueous solution,dehydrated with magnesium sulfate, filtered, and then concentrated toobtain 148 g of concentration residue. The thus-obtained residue waspurified by silica gel chromatography using hexane and chloroform asdeveloping solvents. As a result of analysis, the residue wasbis(3-thietanyl) disulfide (referred to as “compound D” hereinafter).The stability of the thus-obtain compound D was evaluated as ◯ (good).

The identification data of compound D is shown below. TABLE 3 Elementalanalysis C H S Theoretical 34.2% 4.8% 61.0% value Analytical 34.8% 5.1%60.1% value MS spectrum (EI M⁺ = 210 method) IR spectrum 650 cm⁻¹;sulfide ¹H-NMR spectrum a; 3.2 ppm(4H) (CDCL₃) b; 3.5 ppm(4H) c; 4.5ppm(2H) ¹³C-NMR spectrum 1; 33.2 ppm (CDCL₃) 2; 47.5 ppm

EXAMPLE 4

159 g of compound A was charged in a reactor provided with a stirrer andthermometer, and then 300 g of 27% sodium methoxide was added dropwiselyto the compound under stirring at 10° C. After aging at 10° C. for 1hour, the mixture was added dropwisely to a solution of 60 g ofdichloromethane in 100 ml of methanol while the temperature in thereactor was kept at 40° C. After aging at 40° C. for 2 hours, 200 ml oftoluene and 400 ml of water were added for extraction. After an aqueouslayer was removed, the resultant toluene layer was washed twice with asalt aqueous solution, dehydrated with magnesium sulfate, filtered, andthen concentrated to obtain 105 g of concentration residue. Thethus-obtained residue was purified by silica gel chromatography usinghexane and chloroform as developing solvents. As a result of analysis,the residue was bis(3-thietanylthio)methane (referred to as “compound E”hereinafter). The stability of the thus-obtain compound E was evaluatedas ◯ (good).

The identification data of compound E is shown below. TABLE 4 Elementalanalysis C H S Theoretical 37.5% 5.4% 57.1% value Analytical 38.2% 5.6%56.2% value MS spectrum (EI M⁺ = 224 method) IR spectrum 649 cm⁻¹;sulfide 725 cm⁻¹; sulfide ¹H-NMR spectrum a; 3.3 ppm(4H) b; 3.5 ppm(4H)(CDCL₃) c; 3.7 ppm(2H) d; 4.6 ppm(2H) ¹³C-NMR spectrum 1; 33.8 ppm(CDCL₃) 2; 34.4 ppm 3; 42.8 ppm

EXAMPLE 5

159 g of compound A was charged in a reactor provided with a stirrer andthermometer, and then 300 g of 27% sodium methoxide was added dropwiselyto the compound under stirring at 10° C. After aging at 10° C. for 1hour, the mixture was added dropwisely to a solution of 92 g ofbis(chloromethyl) sulfide in 100 ml of methanol while the temperature inthe reactor was kept at 40° C. After aging at 40° C. for 2 hours, 200 mlof toluene and 400 ml of water were added for extraction. After anaqueous layer was removed, the resultant toluene layer was washed twicewith a salt aqueous solution, dehydrated with magnesium sulfate,filtered, and then concentrated to obtain 164 g of concentrationresidue. The thus-obtained residue was purified by silica gelchromatography using hexane and chloroform as developing solvents. As aresult of analysis, the residue was bis(3-thietanylthiomethyl) sulfide(referred to as “compound F” hereinafter). The stability of thethus-obtain compound F was evaluated as ◯ (good).

The identification data of compound F is shown below. TABLE 5 Elementalanalysis C H S Theoretical 35.5% 5.2% 59.3% value Analytical 35.2% 5.5%59.3% value MS spectrum (EI M⁺ = 270 method) IR spectrum 643 cm⁻¹;sulfide 727 cm⁻¹; sulfide ¹H-NMR spectrum a; 3.3 ppm(4H) b; 3.5 ppm(4H)(CDCL₃) c; 3.8 ppm(4H) d; 4.6 ppm(2H) ¹³C-NMR spectrum 1; 33.1 ppm(CDCL₃) 2; 34.3 ppm 3; 42.7 ppm

EXAMPLE 6

159 g of compound A was charged in a reactor provided with a stirrer andthermometer, and then 300 g of 27% sodium methoxide was added dropwiselyto the compound under stirring at 10° C. After aging at 10° C. for 1hour, the mixture was added dropwisely to a solution of 123 g ofm-xylylene dichloride in 100 ml of methanol while the temperature in thereactor was kept at 40° C. After aging at 40° C. for 2 hours, 200 ml oftoluene and 400 ml of water were added for extraction. After an aqueouslayer was removed, the resultant toluene layer was washed twice with asalt aqueous solution, dehydrated with magnesium sulfate, filtered andthen concentrated to obtain 154 g of concentration residue. Thethus-obtained residue was purified by silica gel chromatography usinghexane and chloroform as developing solvents. As a result of analysis,the residue was 1,3-bis(3-thietanylthiomethyl) benzene (referred to as“compound G” hereinafter). The stability of the thus-obtain compound Gwas evaluated as ◯ (good).

The identification data of compound G is shown below. TABLE 6 Elementalanalysis C H S Theoretical 53.4% 5.8% 40.8% value Analytical 53.6% 5.9%40.5% value MS spectrum (EI M⁺ = 314 method) IR spectrum 652 cm⁻¹;sulfide 711, 795 cm⁻¹; m-benzene ring 1604 cm⁻¹; benzene ring ¹H-NMRspectrum a; 3.1 ppm(4H) b; 3.4 ppm(4H) (CDCL₃) c; 3.7 ppm(4H) d; 4.3ppm(2H) e; 7.2 ppm(2H) f; 7.3 ppm(2H) ¹³C-NMR spectrum 1; 34.2 ppm 2;35.3 ppm (CDCL₃) 3; 42.6 ppm 4; 127.5 ppm 5; 128.9 ppm 6; 138.6 ppm

EXAMPLE 7

159 g of compound A was charged in a reactor provided with a stirrer andthermometer, and then 300 g of 27% sodium methoxide was added dropwiselyto the resultant mixture under stirring at 10° C. After aging at 10° C.for 1 hour, the mixture was added dropwisely to a solution of 152 g of2,5-bis(chloromethyl)-1,4-dithiane in 100 ml of methanol while thetemperature in the reactor was kept at 40° C. After aging at 40° C. for2 hours, 200 ml of toluene and 400 ml of water were added forextraction. After an aqueous layer was removed, the resultant toluenelayer was washed twice with a salt aqueous solution, dehydrated withmagnesium sulfate, filtered and then concentrated to obtain 182 g ofconcentration residue. The thus-obtained residue was purified by silicagel chromatography using hexane and chloroform as developing solvents.As a result of analysis, the residue was2,5-bis(3-thietanylthiomethy)-1,4-dithiane (referred to as “compound H”hereinafter). The stability of the thus-obtain compound H was evaluatedas ◯ (good).

The identification data of compound H is shown below. Elemental analysisC H S Theoretical 40.4% 5.6% 54.0% value Analytical 40.1% 5.5% 54.4%value MS spectrum (EI M⁺ = 356 method) IR spectrum 645 cm⁻¹; sulfide 724cm⁻¹; sulfide ¹H-NMR spectrum a; 3.3-3.8 ppm(16H) (CDCL₃) b; 4.2-4.5ppm(4H) ¹³C-NMR spectrum 1; 33.2 ppm 2; 34.4 ppm (CDCL₃) 3; 35.2 ppm 4;41.9 ppm 5; 42.4 ppm

EXAMPLE 8

159 g of compound A and 0.1 g of 49% caustic soda were charged in areactor provided with a stirrer and thermometer, and then 138 g ofepichlorohydrin was added dropwisely to the resultant mixture understirring at 5° C. After aging at 10° C. for 2 hours, 200 ml of toluenewas added, and then 320 g of 25% caustic soda was dropwisely to themixture maintained at 20° C. After aging at 20° C. for 2 hours, anaqueous layer was removed, and then the resultant toluene layer waswashed twice with a salt aqueous solution, dehydrated with magnesiumsulfate, filtered and then concentrated to obtain 238 of concentrationresidue. The residue was 3-(2,3-epoxypropylthio)thietane (referred to as“compound I” hereinafter).

80 g of thiourea, 63 g of acetic acid and 100 g of water were charged ina reactor provided with a stirrer and thermometer, and then 165 g ofcompound I was added dropwisely to the resultant mixture under stirringat 20° C. After aging for 3 hours, 100 ml of toluene was added to themixture, and then 72 g of 25% ammonia water was added dropwisely to themixture maintained at 15° C. After aging 2 hours, an aqueous layer wasremoved, and then the resultant toluene layer was washed twice with asalt aqueous solution, dehydrated with magnesium sulfate, filtered andthen concentrated. The thus-obtained residue was purified by silica gelchromatography using hexane and chloroform as developing solvents. As aresult of analysis, the concentration residue was3-(2,3-epithiopropyltiho) thietane (referred to as “compound J”hereinafter).

The identification data of compound J is shown below. TABLE 8 Elementalanalysis C H S Theoretical 40.5% 5.6% 53.9% value Analytical 41.6% 5.2%53.2% value MS spectrum (EI M⁺ = 178 method) IR spectrum 616 cm⁻¹;episulfide 653 cm⁻¹; sulfide ¹H-NMR spectrum a; 2.2 ppm(1H) b; 2.5ppm(1H) (CDCL₃) c; 2.6 ppm(1H) d; 2.9 ppm(1H) e; 3.0 ppm(1H) f; 3.3ppm(2H) g; 3.4 ppm(2H) h; 4.5 ppm(1H) ¹³C-NMR spectrum 1; 25.8 ppm 2;34.1 ppm (CDCL₃) 3; 34.6 ppm 4; 37.5 ppm 5; 43.3 ppm

EXAMPLE 9

159 g of compound A, 181 g of allyl bromide and 100 ml of methanol werecharged in a reactor provided with a stirrer and thermometer, and then290 g of 28% sodium methoxide was added dropwisely to the resultantmixture under stirring at 5° C. After aging at 10° C. for 2 hours, 500ml of toluene and 1000 ml of water were added. After stirring, anaqueous layer was removed, and then the resultant toluene layer waswashed twice with a salt aqueous solution, dehydrated with magnesiumsulfate, filtered and then concentrated to obtain 198 g of concentrationresidue. The thus-obtained residue was purified by silica gelchromatography using hexane and chloroform as developing solvents. As aresult of analysis, the residue was 3-(allylthio)thietane (referred toas “compound K” hereinafter). The stability of the thus-obtain compoundK was evaluated as ◯ (good).

The identification data of compound K is shown below. TABLE 9 Elementalanalysis C H S Theoretical 49.3% 6.8% 43.8% value Analytical 50.1% 6.6%43.3% value MS spectrum (EI M⁺ = 146 method) IR spectrum 655 cm⁻¹;sulfide 1635 cm⁻¹; allyl 3079 cm⁻¹; allyl 1H-NMR spectrum a; 3.1 ppm(2H)b; 3.2 ppm(2H) (CDCL₃) c; 3.4 ppm(2H) d; 4.3 ppm(1H) e; 5.1 ppm(2H) f;5.8 ppm(1H) ¹³C-NMR spectrum 1; 34.3 ppm 2; 34.6 ppm (CDCL₃) 3; 42.3 ppm4; 117.1 ppm 5; 134.5 ppm

EXAMPLE 10

159 g of compound A and 500 ml of toluene were charged in a reactorprovided with a stirrer and thermometer, and then 180 g of3-chloropropionic chloride and 120 g of pyridine were simultaneouslyadded dropwisely to the resultant mixture under stirring at 35° C. Afteraging at 40° C. for 2 hours, 1000 ml of water was added to the mixture.After stirring, an aqueous layer was removed, and then the resultanttoluene layer was washed twice with water and then dehydrated withmagnesium sulfate. The thus-obtained toluene solution contained3-(3-chloropropionylthio)thietane (referred to as “compound L”hereinafter).

A toluene solution of compound L was charged in a reactor provided witha stirrer and thermometer, and then 150 g of triethylamine was addeddropwisely to the solution under stirring at 20° C. After aging at 25°C. for 2 hours, 100 ml of toluene and 500 ml of water were added. Afterstirring, an aqueous layer was removed, and then the resultant toluenelayer was washed twice with water, dehydrated with magnesium sulfate,filtered and then concentrated to obtain 210 g of concentration residue.The thus-obtained residue was purified by silica gel chromatographyusing hexane and chloroform as developing solvents. As a result ofanalysis, the residue was 3-(acryloylthio)thietane (referred to as“compound M” hereinafter).

The identification data of compound M is shown below. TABLE 10 Elementalanalysis C H O S Theoretical 45.0% 5.0% 10.0% 40.0% value Analytical45.6% 4.8% 11.1% 38.5% value MS spectrum (EI M⁺ = 160 method) IRspectrum 659 cm⁻¹; sulfide 1613 cm⁻¹; acryl 1672 cm⁻¹; thioester ¹H-NMRspectrum a; 3.3 ppm(2H) b; 3.5 ppm(2H) (CDCL₃) c; 5.1 ppm(1H) d; 5.7ppm(1H) e; 6.3 ppm(2H) ¹³C-NMR spectrum 1; 33.8 ppm 2; 39.8 ppm (CDCL₃)3; 127.3 ppm 4; 134.5 ppm 5; 188.8 ppm

EXAMPLE 11

159 g of compound A and 500 ml of toluene were charged in a reactorprovided with a stirrer and thermometer, and then 136 g of methacrylicchloride and 120 g of pyridine were simultaneously added dropwisely tothe resultant mixture under stirring at 10° C. After aging at 10° C. for2 hours, 1000 ml of water was added to the mixture. After stirring, anaqueous layer was removed, and then the resultant toluene layer waswashed twice with water, dehydrated with magnesium sulfate, filtered andthen concentrated to obtain 232 g of concentration residue. Thethus-obtained residue was purified by silica gel chromatography usinghexane and chloroform as developing solvents to obtain 124 g of a liquidmaterial. As a result of analysis, the liquid material was3-(methacyloylthio)thietane (referred to as “compound N” hereinafter).

The identification data of compound N is given blow. TABLE 11 Elementalanalysis C H O S Theoretical 48.2% 5.8% 9.2% 36.8% value Analytical48.6% 5.4% 9.6% 36.4% value MS spectrum (EI M⁺ = 174 method) IR spectrum655 cm⁻¹; sulfide 1617 cm⁻¹; acryl 1663 cm⁻¹; thioester ¹H-NMR spectruma; 1.9 ppm(3H) b; 3.3 ppm(2H) (CDCL₃) c; 3.5 ppm(2H) d; 5.1 ppm(1H) e;5.6 ppm(1H) f; 6.1 ppm(1H) ¹³C-NMR spectrum 1; 17.8 ppm 2; 34.1 ppm(CDCL₃) 3; 40.0 ppm 4; 123.8 ppm 5; 143.2 ppm 6; 191.9 ppm

EXAMPLE 12

106 g of compound A, 500 ml of toluene, and 0.5 g of triethylamine werecharged in a reactor provided with a stirrer and thermometer, and then160 g of compound M was added dropwisely to the resultant mixture understirring at 10° C. After aging at 10° C. for 2 hours, 1000 ml of asodium bicarbonate aqueous solution was added to the mixture. Afterstirring, an aqueous layer was removed, and then the resultant toluenelayer was washed twice with water, dehydrated with magnesium sulfate,filtered and then concentrated to obtain 220 g of concentration residue.The thus-obtained residue was purified by silica gel chromatographyusing hexane and chloroform as developing solvents to obtain 184 g of aliquid material. As a result of analysis, the liquid material was1,3-bis(3-thietanylthio)propane-1-one (referred to as “compound O”hereinafter). The stability of compound O was evaluated as ◯ (good).

The identification data of compound O is shown below. TABLE 12 Elementalanalysis C H O S Theoretical 40.6% 5.3% 6.0% 48.1% value Analytical40.4% 5.2% 6.8% 47.6% value MS spectrum (EI M⁺ = 266 method) IR spectrum658 cm⁻¹; sulfide 1690 cm⁻¹; thioester ¹H-NMR spectrum a; 2.8 ppm(2H) b;2.8 ppm(2H) (CDCL₃) c; 3.2-3.5 ppm(4H) d; 3.4-3.5 ppm (4H) e; 4.4ppm(1H) f; 5.1 ppm(1H) ¹³C-NMR spectrum 1; 25.7 ppm 2; 33.8 ppm (CDCL₃)3; 34.3 ppm 4; 40.0 ppm 5; 43.2 ppm 6; 44.0 ppm 7; 195.8 ppm

EXAMPLE 13

106 g of compound A, 500 ml of toluene, and 0.5 g of triethylamine werecharged in a reactor provided with a stirrer and thermometer, and then174 g of compound N was added dropwisely to the resultant mixture understirring at 10° C. After aging at 10° C. for 2 hours, 1000 ml of asodium bicarbonate aqueous solution was added to the mixture. Afterstirring, an aqueous layer was removed, and then the resultant toluenelayer was washed twice with water, dehydrated with magnesium sulfate,filtered and then concentrated to obtain 224 g of concentration residue.The thus-obtained residue was purified by silica gel chromatographyusing hexane and chloroform as developing solvents to obtain 196 g of aliquid material. As a result of analysis, the liquid material was1,3-bis(3-thietanylthio)-2-methylpropane-1-one (referred to as “compoundP” hereinafter). The stability of compound P was evaluated as ◯ (good).

The identification data of compound P is shown below. TABLE 13 Elementalanalysis C H O S Theoretical 42.8% 5.8% 5.7% 45.7% value Analytical42.4% 5.6% 5.7% 46.3% value MS spectrum (EI M⁺ = 280 method) IR spectrum657 cm⁻¹; sulfide 1686 cm⁻¹; thioester ¹H-NMR spectrum a; 1.2 ppm(3H) b;2.6-2.9 ppm(2H) (CDCL₃) c; 2.7 ppm(1H) d; 3.2-3.4 ppm(4H) e; 3.5 ppm(4H)f; 4.4 ppm(1H) g; 5.1 ppm(1H) ¹³C-NMR spectrum 1; 17.3 ppm 2; 33.8 ppm(CDCL₃) 3; 34.0 ppm 4; 34.4 ppm 5; 40.0 ppm 6; 43.6 ppm 7; 48.8 ppm 8;200.4 ppm

EXAMPLE 14

106 g of compound A was charged in a reactor provided with a stirrer andthermometer, and then 267 g of 15% caustic soda aqueous solution wasadded dropwisely to the compound at 10° C. Then, 125 g of ethylchloroacetate was added dropwisely to the resultant mixture at 10° C.After aging at room temperature for 1 hour, the mixture was separatedinto layers by still standing. After separation, a lower layer was takenout, and dissolved in 500 ml of MeOH, and then 63 g of hydrazine hydratewas added dropwisely to the resultant solution at 10° C. After aging at40° C., the mixture was further stirred at room temperature over onenight. The precipitated crystal was filtered off, and then the resultingfilter cake was dried to obtain 152 g of a white crystal. 150 g of thethus-obtained white crystal was added to 250 g of 15% hydrochloric acid,and then 300 ml of toluene was added to the resultant mixture. Then, 300g of a 30% sodium nitrite aqueous solution was added dropwisely to themixture at 5° C., and then aged. After aging, an organic layer was takenout, dehydrated with magnesium sulfate at 5° C., and then filtered, andthen added to a toluene solution at 80° C. After dropping, the internaltemperature of the reactor was increased to 100° C. for aging. Afteraging, the toluene solution was concentrated to obtain 89 g ofconcentration residue. The thus-obtained concentration residue wassimply distilled to recover 72 g of distillate of 88° C. under 100 Pa.As a result of analysis of the recovered distillate, the distillate was3-(isocyanatomethylthio)thietane (referred to as “compound Q”hereinafter). The stability of compound Q was evaluated as ◯ (good).

The identification data of compound Q is shown below. TABLE 14 Elementalanalysis C H N O S Theoretical 37.2% 4.4% 8.7% 9.9% 39.8% valueAnalytical 37.6% 4.1% 8.9% 9.2% 40.2% value MS spectrum M⁺ = 161 (EImethod) IR spectrum 2241 cm⁻¹; isocyanate ¹H-NMR a; 3.3-3.5 ppm(4H)spectrum b; 4.3 ppm(2H) (CDCL₃) c; 4.6 ppm(1H) ¹³C-NMR 1; 34.4 ppmspectrum 2; 42.9 ppm (CDCL₃) 3; 44.3 ppm

EXAMPLE 15

106 g of compound A was charged in a reactor provided with a stirrer andthermometer, and then 534 g of a 15% caustic soda aqueous solution wasadded dropwisely to the compound at 10° C. Then, an aqueous solution of127 g of chloroethylamine hydrochloride in 200 g of water was addeddropwisely to the mixture at 10° C., and aged at 30° C. for 2 hours.After still standing, 158 g of the separated lower layer was recovered.Then, the recovered lower layer was simply distilled to recover 109 g ofa distillate of 89° C. under 60 Pa. As a result of analysis, therecovered distillate was 3-(aminoethylthio)thietane (referred to as“compound R” hereinafter). The stability of compound R was evaluated as◯ (good).

The identification data of compound R is shown below. TABLE 15 Elementalanalysis C H N S Theoretical 40.2% 7.4%  9.4% 43.0% value Analytical40.6% 7.9% 10.0% 41.5% value MS spectrum (EI M⁺ = 149 method) IRspectrum 1590 cm⁻¹; amine 3361 cm⁻¹; amine ¹H-NMR spectrum a; 1.3ppm(2H) b; 2.7 ppm(2H) (CDCL₃) c; 2.9 ppm(2H) d; 3.2-3.5 ppm(4H) e; 4.4ppm(1H) ¹³C-NMR spectrum 1; 34.6 ppm 2; 35.2 ppm (CDCL₃) 3; 41.7 ppm 4;43.0 ppm

EXAMPLE 16

75 g of compound R and 70 g of a 30% caustic soda aqueous solution werecharged in a reactor provided with a stirrer and thermometer, and then46 g of carbon disulfide was added dropwisely to the resultant mixtureat 40° C. After aging at 70° C. for 1 hour, 200 ml of toluene was addedto the mixture. Then, 57 g of methyl chloroformate was added dropwiselyto the mixture at 50° C., and then aged for 2 hours. Then, the reactionsolution was allowed to stand, and an organic layer was taken out. Theorganic layer was dehydrated with magnesium sulfate, filtered and thenconcentrated to obtain 92 g of concentration residue. The thus-obtainedresidue was simply distilled to recover a distillate of 155° C. under130 Pa. As a result of analysis, the recovered distillate was3-(isothiocyanatoethylthio)thietane (referred to as “compound S”hereinafter). The stability of compound S was evaluated as ◯ (good).

The identification data of compound S is shown below. TABLE 16 Elementalanalysis C H N S Theoretical 37.7% 4.7% 7.3% 50.3% value Analytical36.2% 4.8% 7.6% 51.4% value MS spectrum (EI M⁺ = 191 method) IR spectrum2183-2082 cm⁻¹; isothiocyanate ¹H-NMR spectrum a; 2.6 ppm(2H) b; 3.2-3.4ppm(4H) (CDCL₃) c; 3.3 ppm(2H) d; 4.3 ppm(1H) ¹³C-NMR spectrum 1; 31.4ppm 2; 34.7 ppm (CDCL₃) 3; 43.5 ppm 4; 45.6 ppm 5; 133.0 ppm

EXAMPLE 17

30 g of compound C, 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber, and 0.15 g of dimethyltindichloride as a catalyst were charged in a beaker at room temperature of20° C., and then stirred for 30 minutes to sufficiently dissolve apowder. The resultant mixture was filtered, and then sufficientlydegassed under a reduced pressure of 1.3 kPa or less. The degassedsolution was injected into a mold formed by a glass mold and a tape, andplaced in a polymerization furnace in which the temperature could beprogrammed. Then, the temperature was gradually increased from 30° C. to120° C. to perform polymerization for 20 hours. After the temperaturewas decreased to near room temperature, the glass mold was released toobtain a resin. The thus-obtained resin had excellent transparency andgood appearance with no strain and was colorless.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.701and Abbe's number νe=36, and specific gravity=1.41.

EXAMPLE 18

30 g of compound D, 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber, and 0.15 g of dimethyltindichloride as a catalyst were charged in a beaker at room temperature of20° C., and then stirred for 30 minutes to sufficiently dissolve apowder. The resultant mixture was filtered, and then sufficientlydegassed under a reduced pressure of 1.3 kPa or less. The degassedsolution was injected into a mold formed by a glass mold and a tape, andplaced in a polymerization furnace in which the temperature could beprogrammed. Then, the temperature was gradually increased from 30° C. to120° C. to perform polymerization for 20 hours. After the temperaturewas decreased to near room temperature, the glass mold was released toobtain a resin. The thus-obtained resin had excellent transparency andgood appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.739and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 19

30 g of compound D, 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber, and 0.09 g of trifluoroaceticacid as a catalyst were charged in a beaker at room temperature of 20°C., and then stirred for 30 minutes to sufficiently dissolve a powder.The resultant mixture was filtered, and then sufficiently degassed undera reduced pressure of 1.3 kPa or less. The degassed solution wasinjected into a mold formed by a glass mold and a tape, and placed in apolymerization furnace in which the temperature could be programmed.Then, the temperature was gradually increased from 30° C. to 120° C. toperform polymerization for 20 hours. After the temperature was decreasedto near room temperature, the glass mold was released to obtain a resin.The thus-obtained resin had excellent transparency and good appearancewith no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.738and Abbe's number νe=33, and specific gravity=1.47.

ECAMPLE 20

30 g of compound D, 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber, and 0.15 g oftrifluoromethanesulfonic anhydride as a catalyst were charged in abeaker at room temperature of 20° C. in a nitrogen atmosphere, and thenstirred for 30 minutes to sufficiently dissolve a powder. The resultantmixture was filtered, and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.737and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 21

30 g of compound D, 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber, and 0.15 g of ethyltrifluoromethanesulfonate as a catalyst were charged in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then stirred for 30minutes to sufficiently dissolve a powder. The resultant mixture wasfiltered, and then sufficiently degassed under a reduced pressure of 1.3kPa or less. The degassed solution was injected into a mold formed by aglass mold and a tape, and placed in a polymerization furnace in whichthe temperature could be programmed. Then, the temperature was graduallyincreased from 30° C. to 120° C. to perform polymerization for 20 hours.After the temperature was decreased to near room temperature, the glassmold was released to obtain a resin. The thus-obtained resin hadexcellent transparency and good appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.737and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 22

30 g of compound D and 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber were stirred in a beaker at roomtemperature of 20° C. to form a solution, and then 0.15 g of BF₃.diethyletherate was added as a catalyst to the solution in a nitrogenatmosphere and then sufficiently mixed by stirring. The resultantmixture was filtered to remove an insoluble material, and thensufficiently degassed under a reduced pressure of 1.3 kPa or less. Thedegassed solution was injected into a mold formed by a glass mold and atape, and placed in a polymerization furnace in which the temperaturecould be programmed. Then, the temperature was gradually increased from30° C. to 120° C. to perform polymerization for 20 hours. After thetemperature was decreased to near room temperature, the glass mold wasreleased to obtain a resin. The thus-obtained resin had excellenttransparency and good appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.739and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 23

30 g of compound D and 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber were stirred in a beaker at roomtemperature of 20° C. to form a solution, and then 0.15 g of BF₃.THFcomplex was added as a catalyst to the solution in a nitrogen atmosphereand then sufficiently mixed by stirring. The resultant mixture wasfiltered to remove an insoluble material and then sufficiently degassedunder a reduced pressure of 1.3 kPa or less. The degassed solution wasinjected into a mold formed by a glass mold and a tape, and placed in apolymerization furnace in which the temperature could be programmed.Then, the temperature was gradually increased from 30° C. to 120° C. toperform polymerization for 20 hours. After the temperature was decreasedto near room temperature, the glass mold was released to obtain a resin.The thus-obtained resin had excellent transparency and good appearancewith no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.739and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 24

30 g of compound D and 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber were stirred in a beaker at roomtemperature of 20° C. to form a solution, and then 0.15 g of BF₃.t-butylmethyl ether complex was added as a catalyst to the solution in anitrogen atmosphere and then sufficiently mixed by stirring. Theresultant mixture was filtered to remove an insoluble material and thensufficiently degassed under a reduced pressure of 1.3 kPa or less. Thedegassed solution was injected into a mold formed by a glass mold and atape, and placed in a polymerization furnace in which the temperaturecould be programmed. Then, the temperature was gradually increased from30° C. to 120° C. to perform polymerization for 20 hours. After thetemperature was decreased to near room temperature, the glass mold wasreleased to obtain a resin. The thus-obtained resin had excellenttransparency and good appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.739and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 25

3 g of 4,8-, 4,7- or5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane as an additiveand 0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker atroom temperature of 20° C. in a nitrogen atmosphere, and a solutionformed by stirring 30 g of compound D and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and then sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.735and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 26

3 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and a solution formed bystirring 30 g of compound D and 0.03 g of Viosorb 583 (produced by KyodoChemical Co., Ltd.) as an ultraviolet absorber was added to theresultant mixture and then sufficiently mixed by stirring. Although noinsoluble material was observed in the resultant mixture, the mixturewas filtered and then sufficiently degassed under a reduced pressure of1.3 kPa or less. The degassed solution was injected into a mold formedby a glass mold and a tape, and placed in a polymerization furnace inwhich the temperature could be programmed. Then, the temperature wasgradually increased from 30° C. to 120° C. to perform polymerization for20 hours. After the temperature was decreased to near room temperature,the glass mold was released to obtain a resin. The thus-obtained resinhad excellent transparency and good appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.736and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 27

3 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive, 30 gof compound D, and 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber were stirred in a beaker at roomtemperature of 20° C. to form a solution, and then 0.15 g of BF₃.THFcomplex was added as a curing catalyst and mixed with the solution in anitrogen atmosphere. Although no insoluble material was observed in theresultant mixture, the mixture was filtered and then sufficientlydegassed under a reduced pressure of 1.3 kPa or less. The degassedsolution was injected into a mold formed by a glass mold and a tape, andplaced in a polymerization furnace in which the temperature could beprogrammed. Then, the temperature was gradually increased from 30° C. to120° C. to perform polymerization for 20 hours. After the temperaturewas decreased to near room temperature, the glass mold was released toobtain a resin. The thus-obtained resin had excellent transparency andgood appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.736and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 28

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 9 of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound D and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed. in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.738and Abbe's number νe=33, and specific gravity=1.47.

EXAMPLE 29

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound E and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.721and Abbe's number νe=35, and specific gravity=1.44.

EXAMPLE 30

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound F and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.734and Abbe's number νe=34, and specific gravity=1.45.

EXAMPLE 31

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound G and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.698and Abbe's number νe=30, and specific gravity=1.39.

EXAMPLE 32

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound H and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.702and Abbe's number νe=35, and specific gravity=1.41.

EXAMPLE 33

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound J and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.703and Abbe's number νe=36, and specific gravity=1.41.

EXAMPLE 34

0.15 g of 2-hydroxy-2-methyl-1-phenylpropane-1-one was added as aphotopolymerization initiator to 30 g of compound M in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then sufficientlymixed by stirring. Although no insoluble material was observed in theresultant mixture, the mixture was filtered and then sufficientlydegassed under a reduced pressure of 1.3 kPa or less. The degassedsolution was injected into a mold formed by a glass mold and a tape, andpolymerized by irradiation with ultraviolet rays for 300 seconds using ametal halide lamp (100 W/cm). After the temperature was decreased tonear room temperature after polymerization, the glass mold was releasedto obtain a resin. The thus-obtained resin had excellent transparencyand good appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.661and Abbe's number νe=35, and specific gravity=1.36.

EXAMPLE 35

0.15 g of 2-hydroxy-2-methyl-1-phenylpropane-1-one was added as aphotopolymerization initiator to 30 g of compound N in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then sufficientlymixed by stirring. Although no insoluble material was observed in theresultant mixture, the mixture was filtered and then sufficientlydegassed under a reduced pressure of 1.3 kPa or less. The degassedsolution was injected into a mold formed by a glass mold and a tape, andpolymerized by irradiation with ultraviolet rays for 300 seconds using ametal halide lamp (100 W/cm). After the temperature was decreased tonear room temperature after polymerization, the glass mold was releasedto obtain a resin. The thus-obtained resin had excellent transparencyand good appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.648and Abbe's number νe=36, and specific gravity=1.34.

EXAMPLE 36

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound O and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.684and Abbe's number νe=36, and specific gravity=1.38.

EXAMPLE 37

1.5 g of 1,1,3,3-tetrakis(mercaptomethylthio)propane as an additive and0.15 g of BF₃.THF complex as a catalyst were mixed in a beaker at roomtemperature of 20° C. in a nitrogen atmosphere, and then a solutionformed by stirring 30 g of compound P and 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber wasadded to the resultant mixture and sufficiently mixed by stirring.Although no insoluble material was observed in the resultant mixture,the mixture was filtered and then sufficiently degassed under a reducedpressure of 1.3 kPa or less. The degassed solution was injected into amold formed by a glass mold and a tape, and placed in a polymerizationfurnace in which the temperature could be programmed. Then, thetemperature was gradually increased from 30° C. to 120° C. to performpolymerization for 20 hours. After the temperature was decreased to nearroom temperature, the glass mold was released to obtain a resin. Thethus-obtained resin had excellent transparency and good appearance withno strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.677and Abbe's number νe=37, and specific gravity=1.35.

EXAMPLE 38

14.0 g of compound Q was added to a mixture of 16.0 g of 4,8-, 4,7- or5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 0.015 g ofdibutyltin dichloride and 0.2 g of BF₃.diethyl etherate as a curingcatalyst, 0.03 g of Zelec UN (acidic phosphate) as an internal moldreleasing agent, and 0.03 g of Viosorb 583 (produced by Kyodo ChemicalCo., Ltd.) as an ultraviolet absorber in a beaker at room temperature or20° C. and sufficiently mixed by stirring. After the mixture wasfiltered to remove an insoluble material, the mixture was sufficientlydegassed under a reduced pressure of 1.3 kPa or less. The degassedsolution was injected into a mold formed by a glass mold and a tape, andplaced in a polymerization furnace in which the temperature could beprogrammed. Then, the temperature was gradually increased from 30° C. to120° C. to perform polymerization for 20 hours. After the temperaturewas decreased to near room temperature, the glass mold was released toobtain a resin. The thus-obtained resin had excellent transparency andgood appearance with no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.696and Abbe's number νe=35, and specific gravity=1.43.

EXAMPLE 39

14.2 g of compound Q was added to a mixture of 15.8 g of1,1,3,3-tetrakis(mercaptomethylthio)propane, 0.015 g of dibutyltindichloride and 0.2 g of BF₃.diethyl etherate as a curing catalyst, 0.03g of Zelec UN (acidic phosphate) as an internal mold releasing agent,and 0.03 g of Viosorb 583 (produced by Kyodo Chemical Co., Ltd.) as anultraviolet absorber in a beaker at room temperature or 20° C. andsufficiently mixed by stirring., After the mixture was filtered toremove an insoluble material, the mixture was sufficiently degassedunder a reduced pressure of 1.3 kPa or less. The degassed solution wasinjected into a mold formed by a glass mold and a tape, and placed in apolymerization furnace in which the temperature could be programmed.Then, the temperature was gradually increased from 30° C. to 120° C. toperform polymerization for 20 hours. After the temperature was decreasedto near room temperature, the glass mold was released to obtain a resin.The thus-obtained resin had excellent transparency and good appearancewith no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.726and Abbe's number νe=32, and specific gravity=1.49.

EXAMPLE 40

15.5 g of compound S was added to a mixture of 14.5 g of1,1,3,3-tetrakis(mercaptomethylthio)propane, 0.03 g of dibutyltindichloride and 0.2 g of BF₃.diethyl etherate as a curing catalyst, 0.03g of Zelec UN (acidic phosphate) as an internal mold releasing agent,and 0.03 g of Viosorb 583 (produced by Kyodo Chemical Co., Ltd.) as anultraviolet absorber in a beaker at room temperature or 20° C. andsufficiently mixed by stirring. After the mixture was filtered to removean insoluble material, the mixture was sufficiently degassed under areduced pressure of 1.3 kPa or less. The degassed solution was injectedinto a mold formed by a glass mold and a tape, and placed in apolymerization furnace in which the temperature could be programmed.Then, the temperature was gradually increased from 30° C. to 120° C. toperform polymerization for 20 hours. After the temperature was decreasedto near room temperature, the glass mold was released to obtain a resin.The thus-obtained resin had excellent transparency and good appearancewith no strain.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.753and Abbe's number νe=26, and specific gravity=1.52.

EXAMPLE 41

The lens obtained in each of Examples 23, 25, 26, 38 and 39 was testedwith respect to impact resistance. As a result, the impact resistance ofany of the lenses was evaluated as ◯ (good).

COMPARATIVE EXAMPLE 1

Bis(2,3-epithiopropyl) sulfide (referred to as “compound T” hereinafter)was synthesized as a polyepisulfide compound by the method disclosed inJapanese Unexamined Patent Application Publication No. 9-110979, andthen tested with respect to stability. As a result, the stability wasevaluated as × (not good). 30 g of compound E, 0.03 g of Viosorb 583(produced by Kyodo Chemical Co., Ltd.) as an ultraviolet absorber, and0.15 g of tetrabutylphosphonium bromide as a catalyst were charged in abeaker at room temperature of 20° C., and then stirred for 30 minutes tosufficiently dissolve a powder. The mixture was filtered and thensufficiently degassed under a reduced pressure of 1.3 kPa or less. Thedegassed solution was injected into a mold formed by a glass mold and atape, and placed in a polymerization furnace in which the temperaturecould be programmed. Then, the temperature was gradually increased from30° C. to 120° C. to perform polymerization for 20 hours. After thetemperature was decreased to near room temperature, the glass mold wasreleased to obtain a resin. The thus-obtained resin was transparent.

As a result of measurement of the optical physical properties andspecific gravity of the obtained resin, the refractive index ne=1.704and Abbe's number νe=36, and specific gravity=1.41.

As a result of an impact resistance test of the obtained lens, theimpact resistance was evaluated as × (not good) and inferior to thatevaluated in Example 41.

INDUSTRIAL APPLICABILITY

According to the present invention, an optical material used in ahigh-refractive index field, particularly, a useful compound is obtainedas a substitute with a higher refractive index for a resin produced byusing a polyepisulfide compound as a raw material. The optical materialhas high preservation stability and thus has excellent handleability.Furthermore, a resin produced by using the compound has high opticalphysical properties and high impact resistance, and thus contributes toan increase in refractive index and a decrease in thickness,particularly, in the field of eyeglasses.

1. A sulfur-containing compound having a structure represented byformula (1):

(wherein R1 represents a hydrogen atom, a reactive terminal group, astraight, branched or cyclic alkyl group having 1 to 10 carbon atoms anda reactive terminal group or its thia derivative, an aryl group, or anaralkyl group; Y represents an oxygen atom, a sulfur atom, a seleniumatom, or a tellurium atom; R represents a substituted or unsubstitutedbivalent hydrocarbon group having 1 to 10 carbon atoms, which may bethianated; n represents an integer of 0 to 3; X₁ is substituted for anyone of groups R2 to R7 of a partial structure represented by formula (2)in which the groups R2 to R7 other than the group substituted by X₁ areindependently a hydrogen atom or a substituted or unsubstitutedmonovalent hydrocarbon group having 1 to 10 carbon atoms; and R1 is nota group having a (meth)acryl group when Y is an oxygen atom)


2. The sulfur-containing cyclic compound according to claim 1, thecompound having a structure represented by formula (3):

(wherein R1 represents a hydrogen atom, a reactive terminal group, astraight, branched or cyclic alkyl group having 1 to 10 carbon atoms anda reactive terminal group or its thia derivative, an aryl group, or anaralkyl group; R2 to R6 independently represent a hydrogen atom or asubstituted or unsubstituted monovalent hydrocarbon group having 1 to 10carbon atoms; R represents a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms, which may be thianated; nrepresents an integer of 0 to 3; Y represents an oxygen atom, a sulfuratom, a selenium atom, or a tellurium atom; and R1 is not a group havinga (meth)acryl group when Y is an oxygen atom).
 3. The sulfur-containingcyclic compound according to claim 1, the compound having a structurerepresented by formula (4):

(wherein Q represents a hydrogen atom, a straight, branched or cyclicalkyl group having 1 to 10 carbon atoms and a reactive terminal group orits thia derivative, an aryl group, or an aralkyl group; R represents asubstituted or unsubstituted divalent hydrocarbon group having 1 to 10carbon atoms, which may be thianated; and n represents an integer of 0to 3).
 4. The sulfur-containing cyclic compounds according to claim 1,the compound being any one of 3-mercaptothietane,3-(acryloylthio)thietane, 3-(methacryloylthio)thietane,3-(2,3-epithiopropylthio)thietane, 3-(allylthio)thietane,3-(isocyanatomethylthio)thietane, 3-(aminoethylthio)thietane, and3-(isothiocyanatoethylthio)thietane.
 5. The sulfur-containing compoundsaccording to claim 1, the compound having a structure represented byformula (5):

(wherein R′ and R″ independently represent a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,which may be thianated; U represents a substituted or unsubstitutedstraight, branched or cyclic alkylene group having 1 to 10 carbon atoms,an arylene group, or an aralkylene group, which may be thianated; eachof V and W represents an oxygen atom, a sulfur atom, a selenium atom, ora tellurium atom; I represents an integer of 0 to 2; o represents aninteger of 1 to 4; n1 and n2 independently represent an integer of 0 to3; q represents an integer of 0 or 1; X₂ is substituted for any one ofgroups R9 to R14 of a partial structure represented by formula (6), andX₃ is substituted for any one of groups R15 to R20 of the partialstructure represented by formula (6) in which the groups R9 to R20 otherthan the groups substituted by X₂ and X₃ are independently a hydrogenatom or a substituted or unsubstituted monovalent hydrocarbon grouphaving 1 to 10 carbon atoms)


6. The sulfur-containing cyclic compounds according to claim 1, thecompound being represented by formula (7):

(wherein R9 to R19 independently represent a hydrogen atom , asubstituted or unsubstituted monovalent hydrocarbon group having 1 to 10carbon atoms; R′ and R″ independently represent a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,which may be thianated; U represents a substituted or unsubstitutedstraight, branched or cyclic alkylene group having 1 to 10 carbon atoms,an arylene group, or an aralkylene group, which may be thianated; eachof V and W represents an oxygen atom, a sulfur atom, a selenium atom, ora tellurium atom; I represents an integer of 0 to 2; o represents aninteger of 1 to 4; n1 and n2 independently represent an integer of 0 to3; and q represents an integer of 0 or 1 [[.]]).
 7. Thesulfur-containing cyclic compounds according to claim 1, the compoundbeing represented by formula (8):

(wherein R′″ represents a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms, which may be thianated; Urepresents a substituted or unsubstituted straight, branched or cyclicalkylene group having 1 to 10 carbon atoms, an arylene group, or anaralkylene group, which may be thianated; I represents an integer of 0to 2; o represents an integer of 1 to 4; n represents an integer of 0 to3; and q represents an integer of 0 or 1).
 8. The sulfur-containingcyclic compound according claim 1, the compound being any one ofbis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide,bis(3-thietanylthio) methane, bis(3-thietanylthiomethyl) sulfide,1,4-bis(3-thietanylthiomethyl) benzene, 1,3-bis(thietanylthiomethyl)benzene, 1 ,2-bis(thietanylthiomethyl) benzene,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,1,3-bis(3-thietanylthio)propoane-1-one, and1,3-bis(3-thietanylthio)propane-1-one-2-methyl.
 9. The sulfur-containingcyclic compound according to claim 1, the compound being derived from3-thiethanol and/or 3-halogenothietane and/or 3-mercaptothietane.
 10. Apolymerizable composition containing the compound according to claim 1.11. A resin produced by curing the polymerizable composition accordingto claim
 10. 12. An optical material comprising the resin according toclaim
 11. 13. A method for producing a resin comprisingcast-polymerizing the polymerizable composition according to claim 10.14. A method for producing a resin comprising curing a resin by usingthe polymerizable composition according to claim 10 as a curingcatalyst, and at least one compound selected from boron trihalides andcomplexes thereof, trihalogenomethane sulfonic acids and esters andanhydrides thereof.
 15. A method for producing a resin comprising curinga resin by using the polymerizable composition according to claim 10 asa resin modifier, and at least one compound selected from compounds eachhaving at least one SH group and/or NH group and/or NH2 group.
 16. Thesulfur-containing cyclic compound according claim 2, the compound beingany one of bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide,bis(3-thietanylthio) methane, bis(3-thietanylthiomethyl) sulfide,1,4-bis(3-thietanylthiomethyl) benzene, 1,3-bis(thietanylthiomethyl)benzene, 1,2-bis(thietanylthiomethyl) benzene,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,1,3-bis(3-thietanylthio)propoane-1-one, and1,3-bis(3-thietanylthio)propane-1-one-2-methyl.
 17. Thesulfur-containing cyclic compound according claim 3, the compound beingany one of bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide,bis(3-thietanylthio) methane, bis(3-thietanylthiomethyl) sulfide,1,4-bis(3-thietanylthiomethyl) benzene, 1,3-bis(thietanylthiomethyl)benzene, 1,2-bis(thietanylthiomethyl) benzene,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,1,3-bis(3-thietanylthio)propoane-1-one, and1,3-bis(3-thietanylthio)propane-1-one-2-methyl.
 18. Thesulfur-containing cyclic compound according claim 5, the compound beingany one of bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide,bis(3-thietanylthio) methane, bis(3-thietanylthiomethyl) sulfide,1,4-bis(3-thietanylthiomethyl) benzene, 1,3-bis(thietanylthiomethyl)benzene, 1,2-bis(thietanylthiomethyl) benzene,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,1,3-bis(3-thietanylthio)propoane-1-one, and1,3-bis(3-thietanylthio)propane-1-one-2-methyl.
 19. Thesulfur-containing cyclic compound according claim 6, the compound beingany one of bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide,bis(3-thietanylthio) methane, bis(3-thietanylthiomethyl) sulfide,1,4-bis(3-thietanylthiomethyl) benzene, 1,3-bis(thietanylthiomethyl)benzene, 1,2-bis(thietanylthiomethyl) benzene,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,1,3-bis(3-thietanylthio)propoane-1-one, and1,3-bis(3-thietanylthio)propane-1-one-2-methyl.
 20. Thesulfur-containing cyclic compound according claim 7, the compound beingany one of bis(3-thietanyl) disulfide, bis(3-thietanyl) sulfide,bis(3-thietanylthio) methane, bis(3-thietanylthiomethyl) sulfide,1,4-bis(3-thietanylthiomethyl) benzene, 1,3-bis(thietanylthiomethyl)benzene, 1,2-bis(thietanylthiomethyl) benzene,2,5-bis(3-thietanylthiomethyl)-1,4-dithiane,1,3-bis(3-thietanylthio)propoane-1-one, and1,3-bis(3-thietanylthio)propane-1-one-2-methyl.